**4. Direct methanol fuel cell**

## **4.1. Operation principle**

242 Heat Treatment – Conventional and Novel Applications

FC systems.

been successfully used in both the anode and the cathode in PEMFCs with high cost. Therefore, binary alloy catalysts with Pt are developed for PEMFCs. Thus, Pt-Ni, Pt-Co or Pt-Cr bimetallic nanoparticles can be used as binary alloy catalysts for the significant enhancement of ORR. In particular, the Pt3Ni catalysts of the very high ORR activity are investigated [64-66]. A thin-film rotating disc electrode (TF-RDE) method was used for investigating the electrocatalytic activity of high surface area catalysts, and the highest catalytic activity on Pt/C catalysts towards ORR [67]. In PEMFCs, the catalytic activity and stability of the Pt based catalysts are very important. In the cathode of PEMFCs, Pt based alloy catalysts are developed for PEMFCs. Consequently, the issues of sizes, internal nanostructures, surface nanostructures, shapes and morphologies are also important to the stable operations of PEMFCs for the long periods. In addition, the pt based catalysts with the core-shell nanostructures of the thin Pt shell of around several nanometers have been developed for the next PEMFCs. In particular, the non-Pt catalysts without noble Pt metal are developed. Because noble Pt and Pd metals have the near same catalytic activity of HOR, the Pd based catalysts are studied for the improvements of ORR of PEMFCs [68]. The electro-active sites on carbon nanomaterials electro-catalyzed the reduction of peroxide intermediated from ORR on Pt [69]. The Pd based catalysts can be also used in a combination of Fe, Co, and Cu metals for the improvements of ORR, especially methanol tolerant ORR catalysts. It is clear that stability and durability of the catalysts in the cathodes have importance of the operations of PEMFCs. Therefore, PEMCs can be improved in high stability in the uses of the special supports such as various kinds of carbon supports (e.g. CNTs …). It is clearly admitted that Pt-Ru, Pt-Mo, Pt-Ni catalysts … are used as reformatetolerant catalysts or impure-hydrogen tolerant catalysts for good stability of next PEMFCs. In addition, Pt based ternary catalysts were discussed for the development of various low and high temperature FCs, PEMFCs, and DMFCs involving in their performance, durability and cost [70-73]. Now, an emergence of the hugely urgent demands of the Pt or Pd based catalysts after high heat treatment processes in both low and high temperatures less than 1000 oC, or up to more than 2000 oC offering better characterizations of catalytic activity and stability can be predicted in future due to the catalysts exhibiting the pristine surfaces, shapes and morphologies in the electrode catalysts. The re-constructions, e.g. (111), (110), and (100) planes [10-12], or collapses of the Pt or Pd based nanoparticles and nanostructures with or without heat treatment in the preparation will be very attractive to research and development of new catalysts for PEMFCs and DMFCs [10-12,41]. There are little evidences of the size, structure and morphology of Pt or Pd based catalysts after high heat treatments in media of H2 or N2/H2. These are major challenges in catalysis science, and Pt or Pd based catalysts for FCs, PEMFCs, and DMFCs. Our catalyst preparation gave a better catalytic activity and stability of HER, ORR, and MOR in an environment of mixture H2/N2 avoiding the formation of PtO by heat treatment. In future, the Pt catalysts can be treated at high temperature but their size, nanostructure and morphology in the 10 nm range kept [128- 130]. Therefore, the pure Pt or Pd based catalysts used in the electrodes of FCs, PEMFCs, and DMFCs can give better catalytic activity, stability, and good performance of the whole

In general, PEMFCs can be categorized into various kinds of hydrogen/oxygen FCs, DMFCs, and direct formic acid fuel cells (DFAFC) according to the use of liquid or gas fuels etc. [74- 76]. So far, the economic uses of Pt, Pt-Pd, and Pt-Ru based catalysts as well as catalyst supports have been very crucial to MOR at the anode in DMFCs. To date, methanol can be used in direct chemical-electrical energy conversion in a DMFC in figure 3. The electrochemical reactions occurring in a DMFC are:

$$\text{Anode:}\,\text{CHrOH} + \text{HzO} \rightarrow \text{COr} + \text{6H} + \text{6e} \tag{14}$$

Cathode: 32O2 + 6H+ + 6e- → 3H2O (15)

$$\text{Overall:}\,\text{CHrOH} + \text{@h} \rightarrow \text{COr} + 2\text{HrO} \tag{16}$$

The DMFC is attractive because methanol, being a liquid fuel, is easy to transport and handle. In DMFCs, the MOR mechanism at the anode is crucial. Due to the low operating temperature ~60-150 oC, the Pt based catalysts are sensitive to poisoning. Since CO is formed during electro-oxidation of methanol, CO-tolerant catalysts are used for DMFCs. Nevertheless, these have a much lower power density despite the typically high noble metal loading of the electrodes. In addition, the energy efficiency of DMFCs suffers from high electrode over-potential (voltage losses), and from methanol losses by transfer (by permeation) through the membrane used in DMFCs [77-80].

## **4.2. Catalysts in direct methanol fuel cell**

So far, Pt and Pd catalysts have been known as the most important catalysts for the direct methanol oxidation in electrodes, such as anodes and cathodes. The interesting hydrogen adsorption on Pt or Pd catalyst was studied [81-83]. In this context, PVP and TTAB polymer-Pt nanoparticles were synthesized with the same cubic shape and similar particle size (8.1 and 8.6 nm, respectively). They can be used as the potential Pt catalysts for chemical synthesis [84]. The PVP-Pt nanoparticles of good cubic, tetrahedral, and octahedral morphology in the size range of 10 nm were prepared by polyol method with the use of commercial chemicals for potential catalysts for FCs [85-87]. At such very small scale, the well-controlled synthesis of Pd nanoparticles by polyol synthesis routes using PVP polymer proved that the shapes of Pd NPs provide a good opportunity of investigating their catalytic property [88]. The catalytic reactions of Pt and Pd catalyst have been studied in the different combinations of various metals such as Ru, Rh, and Sn etc. with support materials such as carbon nanomaterials or oxides and glasses in both homogeneous and heterogeneous catalysis [89-97]. The new Pt-monolayer shell electrocatalysts of high stability were developed for the FC cathodes. The role of the Pt shell is to reduce the Pt loading significantly in PEMFCs and DMFCs but synergic effects for enhancing catalytic activity and stability. However, it is very difficult to make the Pt monolayers on the core nanoparticles. Therefore, scientists and researchers have tries to study the easy-to-use chemical and physical methods for highly homogeneous core-shell nanosystems with the use of the thin Pt shells of several nanometers in the size range of 10 nm for PEMFCs and DMFCs. In addition, the good characterization of the engineered nanostructure of the Pt based coreshell nanosystems need to be stabilized after the high heat treatments and preparation processes for obtaining the best catalysts for PEMFCs and DMFCs [98-103], leading to the FC durability up to 200,000 cycles with core-shell catalysts with the Pt-monolayers shells [99]. In all cases, the as-prepared Pt nanoparticles are supported on various carbon nanomaterials for catalytic enhancement. The improvements of Pt catalyst can be performed through by the use of the core-shell nanoparticles or core-shell catalysts that have been proposed. The systems of Pt based, binary, ternary, and quaternary catalysts are proposed in both homogeneous and heterogeneous catalysis [104,105]. Therefore, the Pt based multi-metal catalysts (PtRu or PtRuIr/C) exhibiting high catalytic activities are developed for the MOR [106,107]. A comparison of catalytic activity of Pt, Ru, and PtRu catalysts using Pt(NH3)2(NO2)2 and Ru(NO3)3 precursors for DMFCs was performed. The Pt50Ru50/C catalyst prepared at 200 °C has the maximum electrocatalytic activity toward MOR. The Pt-Ru catalysts have shown the excellent MOR in the stable operations of DMFCs but very high cost [108]. For methanol electro-oxidation, binary, ternary, and quaternary Pt alloy catalysts were prepared. As a result, quaternary alloy catalysts (Pt-Ru-Os-Ir) were considered to be far superior to Pt-Ru in DMFCs [109]. In particular, the successful process of Pt based cubic nanoparticles (Pt-Fe NPs, Pt-Fe-Co NPs), Pt-Fe-Co branched nano cubes, Pt-Fe-Co NPs of low and high Co content was presented. Overall, Pt-Fe-Co branched cubes were used as a good catalyst to show best activity and durability for electrocatalytic MOR [110]. In one study, the evidences of linear sweep voltammetry (LSV) tests indicated that the high peak current density on Pt2Rh/C is about 2.4 times higher than that of Pt/C in alkaline media direct methanol FCs [111]. So far, the Pt-Au catalysts engineering has become very important to the developments of PEMFCs and DMFCs [112]. For the continuous developments of DMFCs, the Pt-Ru alloy and core-shell electrocatalysts for FCs are discussed in a critical survey [113]. The as-prepared catalysts of PtRuMo NPs supported on graphene-carbon nanotubes (G-CNTs) nanocomposites were developed for DMFCs. The results showed that the catalytic activity and stability of the PtRuMo/G-CNTs catalyst are higher than those of PtRuMo/G and PtRuMo/CNTs catalysts. However, the new trends of using Pt based multi-component catalysts without considering the structural issues lead to the complexity of preparation and synthesis [114]. The Pd-Pt catalysts are recognized as potential candidates for PEMFCs and DMFCs operating at low temperatures [115]. Electrocatalytic activity for ORR and oxygen binding energy was intensively studied in the metal catalysts among the different combinations of W, Fe, Mo, Co, Ru, Ni, Rh, Cu, Ir, Pd, Pt, Ag, and Au. According to the oxygen binding energy by density functional theory (DFT), the volcano-type dependence of ORR was discovered in a high catalytic activity of Pt, Pt, Ir, and Ag metal, especially for the very thin Pt and Pd layers as the monolayers. The structural investigation of ORR and oxygen binding energy by the *d*-band model or calculation method of *d*-band center is very crucial to the issues of engineering a novel catalyst [116- 118]. In particular, a X-ray absorption spectroscopy (XAS) method was employed in the

Novel Pt and Pd Based Core-Shell Catalysts with Critical New Issues of Heat Treatment, Stability and Durability for Proton Exchange Membrane Fuel Cells and Direct Methanol Fuel Cells 245

characterization of a number of catalysts for low temperature FCs to determine the existent oxidation state of metal atoms in the catalyst, or in the case of Pt, the d-band vacancy per atom. It is a good tool for confirming the structures of the catalyst *in situ* [119]. There is an important discovery of a synergistic effect to being studied. In theory and practice, synergistic effect needs to be intensively investigated in quantum property in respective to the development of bimetallic catalysts of alloy and core-shell nanostructures. In this context, the synergistic effect of core-shell bimetallic nanoparticles gives an excellent catalytic enhancement. In catalytic activity, the shell provides strongly catalytic sites. The core element gives an electronic effect (a ligand effect) on the shell element because the surface atoms of the shell are coordinated to the core in their catalytic reactions. Therefore, the shell is an important factor to control the catalytic properties. In addition, the core-shell bimetallic structures cause better suppression of adsorbed poisonous species [120,140-143]. This effect is discussed in the metallic NPs of hetero-morphologies and hetero-structures that can be as new types of important catalyst [121]. Of all catalysts, the bimetallic nanoparticles have played important roles in promising applications of catalysis, and FCs [122]. The core-shell nanoparticles and nanostructures were intensively investigated [123- 124]. The Pt-Ni-graphene catalysts were prepared for the high MOR activity observed [125]. In particular, an important role on the MOR activity of Pt-Co and Pt-Ni alloy electrocatalysts for DMFCs has to be ascribed to the degree of alloying [126]. The interaction of Pd NPs and Pd(111) with CH3OH and CH3OH/O2 mixtures was examined from ultrahigh vacuum conditions up to ambient pressures [127]. Here, the particle size and structure dependent effects in methanol oxidation and decomposition are very crucial to the use of the supported Pd catalysts as well as the good incorporation of the pure Pt into various supports with high homogeneous distribution. In addition, we should find suitable heat treatment in good experimental conditions, and Pt based catalyst engineering to increase catalytic activity and

durability.

**Figure 3.** Chemical reactions of direct methanol fuel cell (DMFC)

244 Heat Treatment – Conventional and Novel Applications

Therefore, scientists and researchers have tries to study the easy-to-use chemical and physical methods for highly homogeneous core-shell nanosystems with the use of the thin Pt shells of several nanometers in the size range of 10 nm for PEMFCs and DMFCs. In addition, the good characterization of the engineered nanostructure of the Pt based coreshell nanosystems need to be stabilized after the high heat treatments and preparation processes for obtaining the best catalysts for PEMFCs and DMFCs [98-103], leading to the FC durability up to 200,000 cycles with core-shell catalysts with the Pt-monolayers shells [99]. In all cases, the as-prepared Pt nanoparticles are supported on various carbon nanomaterials for catalytic enhancement. The improvements of Pt catalyst can be performed through by the use of the core-shell nanoparticles or core-shell catalysts that have been proposed. The systems of Pt based, binary, ternary, and quaternary catalysts are proposed in both homogeneous and heterogeneous catalysis [104,105]. Therefore, the Pt based multi-metal catalysts (PtRu or PtRuIr/C) exhibiting high catalytic activities are developed for the MOR [106,107]. A comparison of catalytic activity of Pt, Ru, and PtRu catalysts using Pt(NH3)2(NO2)2 and Ru(NO3)3 precursors for DMFCs was performed. The Pt50Ru50/C catalyst prepared at 200 °C has the maximum electrocatalytic activity toward MOR. The Pt-Ru catalysts have shown the excellent MOR in the stable operations of DMFCs but very high cost [108]. For methanol electro-oxidation, binary, ternary, and quaternary Pt alloy catalysts were prepared. As a result, quaternary alloy catalysts (Pt-Ru-Os-Ir) were considered to be far superior to Pt-Ru in DMFCs [109]. In particular, the successful process of Pt based cubic nanoparticles (Pt-Fe NPs, Pt-Fe-Co NPs), Pt-Fe-Co branched nano cubes, Pt-Fe-Co NPs of low and high Co content was presented. Overall, Pt-Fe-Co branched cubes were used as a good catalyst to show best activity and durability for electrocatalytic MOR [110]. In one study, the evidences of linear sweep voltammetry (LSV) tests indicated that the high peak current density on Pt2Rh/C is about 2.4 times higher than that of Pt/C in alkaline media direct methanol FCs [111]. So far, the Pt-Au catalysts engineering has become very important to the developments of PEMFCs and DMFCs [112]. For the continuous developments of DMFCs, the Pt-Ru alloy and core-shell electrocatalysts for FCs are discussed in a critical survey [113]. The as-prepared catalysts of PtRuMo NPs supported on graphene-carbon nanotubes (G-CNTs) nanocomposites were developed for DMFCs. The results showed that the catalytic activity and stability of the PtRuMo/G-CNTs catalyst are higher than those of PtRuMo/G and PtRuMo/CNTs catalysts. However, the new trends of using Pt based multi-component catalysts without considering the structural issues lead to the complexity of preparation and synthesis [114]. The Pd-Pt catalysts are recognized as potential candidates for PEMFCs and DMFCs operating at low temperatures [115]. Electrocatalytic activity for ORR and oxygen binding energy was intensively studied in the metal catalysts among the different combinations of W, Fe, Mo, Co, Ru, Ni, Rh, Cu, Ir, Pd, Pt, Ag, and Au. According to the oxygen binding energy by density functional theory (DFT), the volcano-type dependence of ORR was discovered in a high catalytic activity of Pt, Pt, Ir, and Ag metal, especially for the very thin Pt and Pd layers as the monolayers. The structural investigation of ORR and oxygen binding energy by the *d*-band model or calculation method of *d*-band center is very crucial to the issues of engineering a novel catalyst [116- 118]. In particular, a X-ray absorption spectroscopy (XAS) method was employed in the characterization of a number of catalysts for low temperature FCs to determine the existent oxidation state of metal atoms in the catalyst, or in the case of Pt, the d-band vacancy per atom. It is a good tool for confirming the structures of the catalyst *in situ* [119]. There is an important discovery of a synergistic effect to being studied. In theory and practice, synergistic effect needs to be intensively investigated in quantum property in respective to the development of bimetallic catalysts of alloy and core-shell nanostructures. In this context, the synergistic effect of core-shell bimetallic nanoparticles gives an excellent catalytic enhancement. In catalytic activity, the shell provides strongly catalytic sites. The core element gives an electronic effect (a ligand effect) on the shell element because the surface atoms of the shell are coordinated to the core in their catalytic reactions. Therefore, the shell is an important factor to control the catalytic properties. In addition, the core-shell bimetallic structures cause better suppression of adsorbed poisonous species [120,140-143]. This effect is discussed in the metallic NPs of hetero-morphologies and hetero-structures that can be as new types of important catalyst [121]. Of all catalysts, the bimetallic nanoparticles have played important roles in promising applications of catalysis, and FCs [122]. The core-shell nanoparticles and nanostructures were intensively investigated [123- 124]. The Pt-Ni-graphene catalysts were prepared for the high MOR activity observed [125]. In particular, an important role on the MOR activity of Pt-Co and Pt-Ni alloy electrocatalysts for DMFCs has to be ascribed to the degree of alloying [126]. The interaction of Pd NPs and Pd(111) with CH3OH and CH3OH/O2 mixtures was examined from ultrahigh vacuum conditions up to ambient pressures [127]. Here, the particle size and structure dependent effects in methanol oxidation and decomposition are very crucial to the use of the supported Pd catalysts as well as the good incorporation of the pure Pt into various supports with high homogeneous distribution. In addition, we should find suitable heat treatment in good experimental conditions, and Pt based catalyst engineering to increase catalytic activity and durability.

**Figure 3.** Chemical reactions of direct methanol fuel cell (DMFC)

### **5. Catalysts and heat treatment**

Of interest to scientists, at present the Pt catalysts are used in both the anode and the cathode in DMFCs. However, the Pt NPs showed a variety of sizes, shapes, and morphologies in the different size ranges. The shapes and morphologies of Pt NPs are synthesized in the forms of cube, octahedra, tetrahedra, plate, wire, flower, rod, fiber etc. The certain issues of their particle sizes are studied in the nanosized ranges of 10 nm, 20 nm, 50 nm etc as well as the homogeneous nucleation, growth, and formation of polyhedral nanoparticles. In particular, the range of the Pt NPs of about 10 nm exhibit the highest catalytic activity with the good morphology and shape such as sphere, cube, octahedra, tetrahedra, and polyhedra etc. The high stability and durability of the shape-dependent catalytic activity are needed to be confirmed in the homogeneity of the particle size in a whole nano-system. In the heat treatments of the Pt NPs, the characterization of size, surface, structure, shape, and morphology of Pt NPs need to be preserved to obtain the Pt catalysts of good catalytic activity, stability, and durability for a long time. The new generations of the Pt-Pd core-shell catalysts with the thin Pd shells of less than several nanometers were developed. They showed the excellent catalytic activity. In our recent research, the Pt NPs of less than 10 nm in size were used as the Pt catalysts, which can be used as the standards for any comparison of catalytic activity of new Pt based catalysts. So far, the heat treatment procedures and methods of heat treatments of the as-prepared metal nanoparticles for catalyst engineering in catalysis have not been considered in their very crucial issues of the size, surface, structure, shape, and morphology. The transformations of structure and property of the as-prepared metal nanoparticles in the ranges of 10 nm and 20 nm through heat treatments or sintering of Pt nanoparticles are very critical to nanoparticles as electro-catalysts or catalytic nanosystems for PEMFCs and DMFCs [128]. We need to confirm that Pt nanoparticles with the rough curved surfaces exhibit catalytic activity much better than Pt nanoparticles with flat and smooth surface through the measurement results. The important effects of heat treatment and the removal of poly(vinylpyrrolidone) (PVP) polymer on electrocatalytic activity of polyhedral Pt NPs towards the ORR mechanism have been investigated. The methods of keeping the size, surface structure, internal structure, shape, and morphology were proposed in our catalyst engineering processes, especially heat treatments of the as-prepared PVP-Pt nanoparticles at 300 oC. The loaded electrodes were carefully dried in air for 3 h at 25 °C and heated with the heating rate of 1 °C/min up to 450 °C in air and a keeping time of 2 h in order to remove any organic species. The pure Pt nanoparticles need to be kept in their good characterization of size and morphology in the size range of 10 nm. We proposed that the polyhedral Pt NPs of around 10 nm can be used the standard Pt catalyst in all research of electrocatalysts in PEMFCs and DMFCs due to their higher concentration of surface steps, kinks, islands, terraces, and corners [129-137]. In our research, Pt-Au NPs were prepared by polyol method, which can be used as Pt-Au catalysts for DMFCs [138]. In particular, Pt-Pd alloy and core-shell NPs were synthesized by polyol method. The core-shell NPs can be used for low temperature PEMFCs and DMFCs for the excellent advantages of reducing the Pt total metal weight. Therefore, it is an economic solution of the suitable use of Pt based core-shell catalysts for next FCs. The new

Novel Pt and Pd Based Core-Shell Catalysts with Critical New Issues of Heat Treatment, Stability and Durability for Proton Exchange Membrane Fuel Cells and Direct Methanol Fuel Cells 247

Pt monolayer Pd-Au catalyst of a core-shell structure with double shells was found in a good stability and activity of ORR. The double shells have an outermost shell of Pt monolayer and a sub-layer shell of Pd-Au alloy [139,140]. In our new results and findings, new evidence of fast enhancement of ORR on the electrode of the new Pt-Pd core-shell catalyst in the size range of 25 nm is clearly observed in a comparison with the prepared Pt catalyst in the size range of 10 nm. Therefore, it is important to use core-shell bimetallic catalysts to increase the ORR rate in the electrode catalyst. For the case of Pt-Pd core-shell catalysts, the fast hydrogen-desorption response and high sensitivity in our results after reaching the stable characterization after only the first CV cycle in a comparison to Pt catalyst. This enables the realization of robust and efficient Pt- or Pd-based core-shell catalysts that are extremely sensitive to the fast hydrogen desorption. Most of the alternative method of improving the hydrogen reaction by the core-shell nanostructures can be clearly realized. During the measurement, the electrodes are swept from -0.2 to 1.0 V with respective to the kinds of saturated standard electrodes. There are the specific regions in the cyclic voltammogram (Figures 4 and 5). They show highly and good catalytic activity and surface kinetics for the case of both the Pt catalysts of 10 nm and the Pt-Pd core-shell catalysts of 25 nm. It is clear that the high heat treatments of our catalyst preparation in H2/N2 offer the good characterization of the size, surface, structure, and morphology. Therefore, the highly long-term catalytic activity, stability, and durability in chemical and physical Pt or Pd based catalysts are needed in the catalyst layers of FCs, DMFCs, and PEMFCs. The effects of using a suitable temperature range in heat treatment should be suitable to various FCs, for example the better ORR activity. This depends on the operating temperature of various FCs. They were characterized by the chemical activity occurring at the electrode surface. In the forward sweep, the first region assigned to hydrogen desorption is crucial to confirm catalytic activity of the Pt catalysts. The slow kinetics of hydrogen desorption of the case of Pt catalyst was confirmed in the cell before the stabilization of CV was achieved from the first cycle to the twentieth cycle, and the fast kinetics of hydrogen desorption of the case of Pt-Pd core-shell catalyst. Indeed, the results proved the good desorption and adsorption of hydrogen of both Pt catalysts and Pt-Pd coreshell catalyst as evidences of good catalytic activity of two kinds of important catalysts in the preparation process and heat treatment in figures 4 and 5. To evaluate the catalytic activity of the prepared catalysts, the electrochemical active surface area (ECSA) of the Pt catalyst is calculated to be (10.5 m2g-1) in a comparison with that of the Pt-Pd core-shell catalysts (27.7 m2g-1) in our catalytic investigations. Thus, suitable heat treatments or sintering processes of the Pt or Pd based catalysts for obtaining good catalytic activity and stability in the desirable nano and micro structures are very crucial to enhance, and improve the continuous operation of direct chemical-into-electrical energy conversion, high stability and durability of various FCs, PEMFCs and DMFCs for the urgent global challenges of energy and environment. Obviously, the heat treatments can lead to significantly reduce the effects of CO poisoning to the electrodes in PEMFCs and DMFCs. One of the most challenging goals in the heat treatment is to develop successful protocols for keeping the good characterization of the as-preparation Pt NPs such as surface, structure, size, and shape in their nanosized ranges. In our research, the polyol method was used for our 246 Heat Treatment – Conventional and Novel Applications

**5. Catalysts and heat treatment** 

Of interest to scientists, at present the Pt catalysts are used in both the anode and the cathode in DMFCs. However, the Pt NPs showed a variety of sizes, shapes, and morphologies in the different size ranges. The shapes and morphologies of Pt NPs are synthesized in the forms of cube, octahedra, tetrahedra, plate, wire, flower, rod, fiber etc. The certain issues of their particle sizes are studied in the nanosized ranges of 10 nm, 20 nm, 50 nm etc as well as the homogeneous nucleation, growth, and formation of polyhedral nanoparticles. In particular, the range of the Pt NPs of about 10 nm exhibit the highest catalytic activity with the good morphology and shape such as sphere, cube, octahedra, tetrahedra, and polyhedra etc. The high stability and durability of the shape-dependent catalytic activity are needed to be confirmed in the homogeneity of the particle size in a whole nano-system. In the heat treatments of the Pt NPs, the characterization of size, surface, structure, shape, and morphology of Pt NPs need to be preserved to obtain the Pt catalysts of good catalytic activity, stability, and durability for a long time. The new generations of the Pt-Pd core-shell catalysts with the thin Pd shells of less than several nanometers were developed. They showed the excellent catalytic activity. In our recent research, the Pt NPs of less than 10 nm in size were used as the Pt catalysts, which can be used as the standards for any comparison of catalytic activity of new Pt based catalysts. So far, the heat treatment procedures and methods of heat treatments of the as-prepared metal nanoparticles for catalyst engineering in catalysis have not been considered in their very crucial issues of the size, surface, structure, shape, and morphology. The transformations of structure and property of the as-prepared metal nanoparticles in the ranges of 10 nm and 20 nm through heat treatments or sintering of Pt nanoparticles are very critical to nanoparticles as electro-catalysts or catalytic nanosystems for PEMFCs and DMFCs [128]. We need to confirm that Pt nanoparticles with the rough curved surfaces exhibit catalytic activity much better than Pt nanoparticles with flat and smooth surface through the measurement results. The important effects of heat treatment and the removal of poly(vinylpyrrolidone) (PVP) polymer on electrocatalytic activity of polyhedral Pt NPs towards the ORR mechanism have been investigated. The methods of keeping the size, surface structure, internal structure, shape, and morphology were proposed in our catalyst engineering processes, especially heat treatments of the as-prepared PVP-Pt nanoparticles at 300 oC. The loaded electrodes were carefully dried in air for 3 h at 25 °C and heated with the heating rate of 1 °C/min up to 450 °C in air and a keeping time of 2 h in order to remove any organic species. The pure Pt nanoparticles need to be kept in their good characterization of size and morphology in the size range of 10 nm. We proposed that the polyhedral Pt NPs of around 10 nm can be used the standard Pt catalyst in all research of electrocatalysts in PEMFCs and DMFCs due to their higher concentration of surface steps, kinks, islands, terraces, and corners [129-137]. In our research, Pt-Au NPs were prepared by polyol method, which can be used as Pt-Au catalysts for DMFCs [138]. In particular, Pt-Pd alloy and core-shell NPs were synthesized by polyol method. The core-shell NPs can be used for low temperature PEMFCs and DMFCs for the excellent advantages of reducing the Pt total metal weight. Therefore, it is an economic solution of the suitable use of Pt based core-shell catalysts for next FCs. The new Pt monolayer Pd-Au catalyst of a core-shell structure with double shells was found in a good stability and activity of ORR. The double shells have an outermost shell of Pt monolayer and a sub-layer shell of Pd-Au alloy [139,140]. In our new results and findings, new evidence of fast enhancement of ORR on the electrode of the new Pt-Pd core-shell catalyst in the size range of 25 nm is clearly observed in a comparison with the prepared Pt catalyst in the size range of 10 nm. Therefore, it is important to use core-shell bimetallic catalysts to increase the ORR rate in the electrode catalyst. For the case of Pt-Pd core-shell catalysts, the fast hydrogen-desorption response and high sensitivity in our results after reaching the stable characterization after only the first CV cycle in a comparison to Pt catalyst. This enables the realization of robust and efficient Pt- or Pd-based core-shell catalysts that are extremely sensitive to the fast hydrogen desorption. Most of the alternative method of improving the hydrogen reaction by the core-shell nanostructures can be clearly realized. During the measurement, the electrodes are swept from -0.2 to 1.0 V with respective to the kinds of saturated standard electrodes. There are the specific regions in the cyclic voltammogram (Figures 4 and 5). They show highly and good catalytic activity and surface kinetics for the case of both the Pt catalysts of 10 nm and the Pt-Pd core-shell catalysts of 25 nm. It is clear that the high heat treatments of our catalyst preparation in H2/N2 offer the good characterization of the size, surface, structure, and morphology. Therefore, the highly long-term catalytic activity, stability, and durability in chemical and physical Pt or Pd based catalysts are needed in the catalyst layers of FCs, DMFCs, and PEMFCs. The effects of using a suitable temperature range in heat treatment should be suitable to various FCs, for example the better ORR activity. This depends on the operating temperature of various FCs. They were characterized by the chemical activity occurring at the electrode surface. In the forward sweep, the first region assigned to hydrogen desorption is crucial to confirm catalytic activity of the Pt catalysts. The slow kinetics of hydrogen desorption of the case of Pt catalyst was confirmed in the cell before the stabilization of CV was achieved from the first cycle to the twentieth cycle, and the fast kinetics of hydrogen desorption of the case of Pt-Pd core-shell catalyst. Indeed, the results proved the good desorption and adsorption of hydrogen of both Pt catalysts and Pt-Pd coreshell catalyst as evidences of good catalytic activity of two kinds of important catalysts in the preparation process and heat treatment in figures 4 and 5. To evaluate the catalytic activity of the prepared catalysts, the electrochemical active surface area (ECSA) of the Pt catalyst is calculated to be (10.5 m2g-1) in a comparison with that of the Pt-Pd core-shell catalysts (27.7 m2g-1) in our catalytic investigations. Thus, suitable heat treatments or sintering processes of the Pt or Pd based catalysts for obtaining good catalytic activity and stability in the desirable nano and micro structures are very crucial to enhance, and improve the continuous operation of direct chemical-into-electrical energy conversion, high stability and durability of various FCs, PEMFCs and DMFCs for the urgent global challenges of energy and environment. Obviously, the heat treatments can lead to significantly reduce the effects of CO poisoning to the electrodes in PEMFCs and DMFCs. One of the most challenging goals in the heat treatment is to develop successful protocols for keeping the good characterization of the as-preparation Pt NPs such as surface, structure, size, and shape in their nanosized ranges. In our research, the polyol method was used for our

synthesis of the Pt and Pd bimetallic nanoparticles with alloy and core-shell structure. In comparison, we also can control the time and temperature of convenient heat-treatments to the pure Pt or Pt/support catalysts for their better catalytic activity. Clearly, the temperature plays an important role in heat treatments for making the better Pt based catalysts. The shape and morphology of polyhedral-like or spherical-like Pt nanoparticles are crucial in the further study of electro-catalytic activity.

Novel Pt and Pd Based Core-Shell Catalysts with Critical New Issues of Heat Treatment, Stability and Durability for Proton Exchange Membrane Fuel Cells and Direct Methanol Fuel Cells 249

**Figure 5.** (a)-(f) TEM and HRTEM images of the as-prepared Pt-Pd core-shell. The thin Pd shells protect polyhedral Pt cores. The nucleation and growth of Pd shells are controlled by a chemical synthesis. Scale bars: (a)-(c) 20 nm. (d) 5 nm. (e) 5 nm. (f) 2 nm. (h) Schematic of a standard three-electrode electrochemical cell. Reprinted from: Long NV, Ohtaki M, Hien TD, Randy J, Nogami M, Electrochim.

Acta. 56:9133-9143. Copyright 2011 with permission from Elsevier [140]

**Figure 4.** TEM images of the polyhedral Pt nanoparticles. Scale bars: (a)-(d) 20 nm. (e) Cyclic voltammograms of the pure Pt catalysts in 0.5 M H2SO4 from -0.2 V to 1.0 V. Reprinted from: Long NV, Ohtaki M, Hien TD, Randy J, Nogami M, Electrochim. Acta. 56:9133-9143. Copyright 2011 with permission from Elsevier [140]

It means that the high heat treatment to the as-prepared Pt nanoparticles for the good catalyst can be performed in the ways with various solvents or pure water during their preparation. However, the desirable characterization of size, shape, morphology, and structure need to be kept for the better catalytic activity. Therefore, scientists need provide more research results of Pt based catalysts with heat treatment effects in electro-catalysis. Thus, new Pt based catalysts, electrodes, and membranes need to be considerably studied for the reduction of their high costs but the high whole performance. The effects of heat treatments on size, shape, surface, and structure of the pure Pt nanoparticles (pure Pt catalyst) or Pt based catalysts for catalytic activity, durability and stability can be intensively analyzed by *in situ* TEM and electrochemical measurements as well as the chemical reactions and their kinetics at the surfaces of the only Pt catalyst or Pt/support catalysts in fuel cells.

In electrochemical measurements, we can use electrolyte solution of using 0.5 M H2SO4+1.0 M CH3OH (a scan rate of 50 mV s-1). Our comparisons of cyclic voltammograms were done between the pure Pt catalysts in the nanosized range of 10 nm, and the pure Pt-Pd core-shell catalysts in the nanosized range of 25 nm in the mixture of 0.5 M H2SO4 and 1 M CH3OH in figure 6. A stable voltammogram was attained after 20 cycles of sweeping between 0 and 1 V. Two oxidation peaks are observed. The good MOR was confirmed in the evidences of the typical peaks at 0.6 V and 0.8 V in the forward sweep, and the other peaks at 0.4 and 0.5 V in

Novel Pt and Pd Based Core-Shell Catalysts with Critical New Issues of Heat Treatment, Stability and Durability for Proton Exchange Membrane Fuel Cells and Direct Methanol Fuel Cells 249

248 Heat Treatment – Conventional and Novel Applications

the further study of electro-catalytic activity.

permission from Elsevier [140]

synthesis of the Pt and Pd bimetallic nanoparticles with alloy and core-shell structure. In comparison, we also can control the time and temperature of convenient heat-treatments to the pure Pt or Pt/support catalysts for their better catalytic activity. Clearly, the temperature plays an important role in heat treatments for making the better Pt based catalysts. The shape and morphology of polyhedral-like or spherical-like Pt nanoparticles are crucial in

**Figure 4.** TEM images of the polyhedral Pt nanoparticles. Scale bars: (a)-(d) 20 nm. (e) Cyclic

surfaces of the only Pt catalyst or Pt/support catalysts in fuel cells.

voltammograms of the pure Pt catalysts in 0.5 M H2SO4 from -0.2 V to 1.0 V. Reprinted from: Long NV, Ohtaki M, Hien TD, Randy J, Nogami M, Electrochim. Acta. 56:9133-9143. Copyright 2011 with

It means that the high heat treatment to the as-prepared Pt nanoparticles for the good catalyst can be performed in the ways with various solvents or pure water during their preparation. However, the desirable characterization of size, shape, morphology, and structure need to be kept for the better catalytic activity. Therefore, scientists need provide more research results of Pt based catalysts with heat treatment effects in electro-catalysis. Thus, new Pt based catalysts, electrodes, and membranes need to be considerably studied for the reduction of their high costs but the high whole performance. The effects of heat treatments on size, shape, surface, and structure of the pure Pt nanoparticles (pure Pt catalyst) or Pt based catalysts for catalytic activity, durability and stability can be intensively analyzed by *in situ* TEM and electrochemical measurements as well as the chemical reactions and their kinetics at the

In electrochemical measurements, we can use electrolyte solution of using 0.5 M H2SO4+1.0 M CH3OH (a scan rate of 50 mV s-1). Our comparisons of cyclic voltammograms were done between the pure Pt catalysts in the nanosized range of 10 nm, and the pure Pt-Pd core-shell catalysts in the nanosized range of 25 nm in the mixture of 0.5 M H2SO4 and 1 M CH3OH in figure 6. A stable voltammogram was attained after 20 cycles of sweeping between 0 and 1 V. Two oxidation peaks are observed. The good MOR was confirmed in the evidences of the typical peaks at 0.6 V and 0.8 V in the forward sweep, and the other peaks at 0.4 and 0.5 V in

**Figure 5.** (a)-(f) TEM and HRTEM images of the as-prepared Pt-Pd core-shell. The thin Pd shells protect polyhedral Pt cores. The nucleation and growth of Pd shells are controlled by a chemical synthesis. Scale bars: (a)-(c) 20 nm. (d) 5 nm. (e) 5 nm. (f) 2 nm. (h) Schematic of a standard three-electrode electrochemical cell. Reprinted from: Long NV, Ohtaki M, Hien TD, Randy J, Nogami M, Electrochim. Acta. 56:9133-9143. Copyright 2011 with permission from Elsevier [140]

Novel Pt and Pd Based Core-Shell Catalysts with Critical New Issues of Heat Treatment, Stability and Durability for Proton Exchange Membrane Fuel Cells and Direct Methanol Fuel Cells 251

promising properties in catalysis, biology and medicine. According to our research, the effects of the nanostructures can be confirmed in the better catalytic activity. In general, the Frank-van der Merwe (FM), Volmer-Weber (VW), and Stranski-Krastanov (SK) growth modes show the formation of various nanostructures of core-shell nanoparticles [141], such as core-shell bimetallic NPs and oxide-metal NPs [104,141]. It is clear that the formations of novel Pt based core-shell bimetallic nanoparticles the thin-based metal or alloy shells can be controlled in both the FM and SK growth modes for the utilization of Pt metal. The FM overgrowth mode or the epitaxial overgrowth of the thin Pt shells on the metal or oxide cores due to the layer-by-layer mechanism are very crucial to discover most of new Pt based core-shell catalysts for FCs, such as PEMFCs or DMFCs. The core-shell engineered nanoparticles in the nanosized ranges of about 10 nm and 20 nm with the Pt metal shell or the Pt based bimetallic shells or the Pt based multi-metallic shells become an important topic of next research and scientific investigations for FCs. The thin shells can be noble metals such as Pt, Pt-Au, Pt-Pd, Pt based alloys with the use of Ag, Au, Rh, Ru, and Pd metal. The thick cores can be cheap metals such as Ni, Co, Fe, Cu .. and alloys, even and ceramics and glasses. With regards to low-cost issues, we suggest that typical core-shell configurations of bimetallic nanoparticles are proposed in the main goals of designing Pt and Pd based catalysts with the shells of using ultra-low mass of Pt metal or Pt-noble (Pd, Ru, Rh, Au, Ag) bimetals [140-143, 190]. Thus, a variety of the core-shell configurations with the thin Pt shell or the thin Pt based bimetallic shells controllably created in chemical and physical engineering is one of the best ways of the realization of large-scale commercialization and development of FCs, such as PEMFCs and DMFCs. We suggest that noble Au NPs can be used the good core for the Pt shells for DMFCs and PEMFCs. In most cases, Pt-based bimetallic NPs were supported on carbon nanomaterials such as MWCNTs for the catalytic enhancement in the operations of various DMFCs due to their large surface area and good conductivity [145,146]. In addition, the Co-Pt core-shell nanoparticles can be used as potential catalysts in cathode of PEMFCS because of their high stability and durability [147- 149]. In many efforts, the catalysts such as Pt-Pd, Pt-Ru, Pt-Rh and Pt-Sn/C exhibiting an improved performance in MOR as anode materials were prepared by ultrasonic method [150,151]. Importantly, the catalytic properties of well-characterized Ru-Pt core-shell NPs were demonstrated for preferential CO oxidation [152]. The metal-oxide nanostructures of Pd or Pt metals and TiO2 or Zr2O3 oxides by self-assembly are proposed for catalysis and FCs. The core-shell nanoparticles and nanostructures will offer potentially promising applications in homogeneous and heterogeneous catalysis, biology and medicine [153,154]. The recent developments of polymer electrolyte membranes for FCs were discussed for improving the long-term stability [155]. The new methanol-tolerant catalysts with the use of Pd nano cubes exhibiting high electro-activity for ORR in the 0.5 M H2SO4 solution were confirmed [156,157]. Thus far, the catalysts with the use of the Pt-Pd nanoparticles or the Pt-Pd nanostructures of various size, internal structure, surface structure, shape, morphology, and composition by various preparation methods have been intensively studied for practical applications in various FCs, PEMFCs, and DMFCs. There are the very huge demands of high-surface area catalysts of Pt-Pd NPs supported on carbon nanomaterials that have been used in various FCs, PEMFCs and PEMCs [158-170,188,189]. The nano-porous SiO2 solids

**Figure 6.** (a) Cyclic voltammogram of Pt catalysts, and Pt-Pd core-shell catalysts on glassy carbon electrode in N2-bubbled 0.5 M H2SO4 electrolyte (scan rate: 50 mV s-1). (b) Cyclic voltammogram towards methanol electro-oxidation of Pt catalyst and Pt-Pd core-shell catalyst. (c) Simple pathways of MOR (A). Possible reaction pathways of MOR (B). (d) Chronoamperometry data of Pt and Pt-Pd catalysts in 0.5 M H2SO4+1.0 M CH3OH and polarization potential about 0.5 V. Reprinted from: Long NV, Ohtaki M, Hien TD, Randy J, Nogami M, Electrochim. Acta. 56:9133-9143. Copyright 2011 with permission from Elsevier [140]

the backward sweep. Our results of the MOR mechanisms showed that the two peaks are directly related to methanol oxidation and the associated intermediates. The fascinating high stable characterization was observed for Pt-Pd core-shell catalysts. They showed a very high initial current about 1.29×10-3 A cm-2 in comparison with the Pt catalyst of initial current about 4.33×10-4 A cm-2. In all our research, the samples with the Pt or Pt based catalysts were carried out in the heat treatment procedures at 300 oC and up to 450 oC. The loaded electrodes were dried in air for 3 h at 25 °C and heated with the heating rate of 1 °C/min up to 450 °C in air and a keeping time of about 2 h for the complete removal of any organic species. After heat treatment, the specific size, shape, structure and morphology of Pt nanoparticles were retained in the good conditions of the Pt based catalyst for the CV measurements [141-143]. New hydrogen absorption was found in the Pt-Pd bimetallic nanoparticles [144]. In our research, we suggested that there are the relationships and dependences of electro-catalytic properties on issues of size, internal structure and surface structure, shape and morphology, and composition of Pt or Pd based catalysts in catalysis, biology, and medicine. The homogeneous properties of size, internal structure and surface structure, shape and morphology, and composition of nanoparticles can create novel and 250 Heat Treatment – Conventional and Novel Applications

permission from Elsevier [140]

**Figure 6.** (a) Cyclic voltammogram of Pt catalysts, and Pt-Pd core-shell catalysts on glassy carbon electrode in N2-bubbled 0.5 M H2SO4 electrolyte (scan rate: 50 mV s-1). (b) Cyclic voltammogram towards methanol electro-oxidation of Pt catalyst and Pt-Pd core-shell catalyst. (c) Simple pathways of MOR (A). Possible reaction pathways of MOR (B). (d) Chronoamperometry data of Pt and Pt-Pd catalysts in 0.5 M H2SO4+1.0 M CH3OH and polarization potential about 0.5 V. Reprinted from: Long NV, Ohtaki M, Hien TD, Randy J, Nogami M, Electrochim. Acta. 56:9133-9143. Copyright 2011 with

the backward sweep. Our results of the MOR mechanisms showed that the two peaks are directly related to methanol oxidation and the associated intermediates. The fascinating high stable characterization was observed for Pt-Pd core-shell catalysts. They showed a very high initial current about 1.29×10-3 A cm-2 in comparison with the Pt catalyst of initial current about 4.33×10-4 A cm-2. In all our research, the samples with the Pt or Pt based catalysts were carried out in the heat treatment procedures at 300 oC and up to 450 oC. The loaded electrodes were dried in air for 3 h at 25 °C and heated with the heating rate of 1 °C/min up to 450 °C in air and a keeping time of about 2 h for the complete removal of any organic species. After heat treatment, the specific size, shape, structure and morphology of Pt nanoparticles were retained in the good conditions of the Pt based catalyst for the CV measurements [141-143]. New hydrogen absorption was found in the Pt-Pd bimetallic nanoparticles [144]. In our research, we suggested that there are the relationships and dependences of electro-catalytic properties on issues of size, internal structure and surface structure, shape and morphology, and composition of Pt or Pd based catalysts in catalysis, biology, and medicine. The homogeneous properties of size, internal structure and surface structure, shape and morphology, and composition of nanoparticles can create novel and promising properties in catalysis, biology and medicine. According to our research, the effects of the nanostructures can be confirmed in the better catalytic activity. In general, the Frank-van der Merwe (FM), Volmer-Weber (VW), and Stranski-Krastanov (SK) growth modes show the formation of various nanostructures of core-shell nanoparticles [141], such as core-shell bimetallic NPs and oxide-metal NPs [104,141]. It is clear that the formations of novel Pt based core-shell bimetallic nanoparticles the thin-based metal or alloy shells can be controlled in both the FM and SK growth modes for the utilization of Pt metal. The FM overgrowth mode or the epitaxial overgrowth of the thin Pt shells on the metal or oxide cores due to the layer-by-layer mechanism are very crucial to discover most of new Pt based core-shell catalysts for FCs, such as PEMFCs or DMFCs. The core-shell engineered nanoparticles in the nanosized ranges of about 10 nm and 20 nm with the Pt metal shell or the Pt based bimetallic shells or the Pt based multi-metallic shells become an important topic of next research and scientific investigations for FCs. The thin shells can be noble metals such as Pt, Pt-Au, Pt-Pd, Pt based alloys with the use of Ag, Au, Rh, Ru, and Pd metal. The thick cores can be cheap metals such as Ni, Co, Fe, Cu .. and alloys, even and ceramics and glasses. With regards to low-cost issues, we suggest that typical core-shell configurations of bimetallic nanoparticles are proposed in the main goals of designing Pt and Pd based catalysts with the shells of using ultra-low mass of Pt metal or Pt-noble (Pd, Ru, Rh, Au, Ag) bimetals [140-143, 190]. Thus, a variety of the core-shell configurations with the thin Pt shell or the thin Pt based bimetallic shells controllably created in chemical and physical engineering is one of the best ways of the realization of large-scale commercialization and development of FCs, such as PEMFCs and DMFCs. We suggest that noble Au NPs can be used the good core for the Pt shells for DMFCs and PEMFCs. In most cases, Pt-based bimetallic NPs were supported on carbon nanomaterials such as MWCNTs for the catalytic enhancement in the operations of various DMFCs due to their large surface area and good conductivity [145,146]. In addition, the Co-Pt core-shell nanoparticles can be used as potential catalysts in cathode of PEMFCS because of their high stability and durability [147- 149]. In many efforts, the catalysts such as Pt-Pd, Pt-Ru, Pt-Rh and Pt-Sn/C exhibiting an improved performance in MOR as anode materials were prepared by ultrasonic method [150,151]. Importantly, the catalytic properties of well-characterized Ru-Pt core-shell NPs were demonstrated for preferential CO oxidation [152]. The metal-oxide nanostructures of Pd or Pt metals and TiO2 or Zr2O3 oxides by self-assembly are proposed for catalysis and FCs. The core-shell nanoparticles and nanostructures will offer potentially promising applications in homogeneous and heterogeneous catalysis, biology and medicine [153,154]. The recent developments of polymer electrolyte membranes for FCs were discussed for improving the long-term stability [155]. The new methanol-tolerant catalysts with the use of Pd nano cubes exhibiting high electro-activity for ORR in the 0.5 M H2SO4 solution were confirmed [156,157]. Thus far, the catalysts with the use of the Pt-Pd nanoparticles or the Pt-Pd nanostructures of various size, internal structure, surface structure, shape, morphology, and composition by various preparation methods have been intensively studied for practical applications in various FCs, PEMFCs, and DMFCs. There are the very huge demands of high-surface area catalysts of Pt-Pd NPs supported on carbon nanomaterials that have been used in various FCs, PEMFCs and PEMCs [158-170,188,189]. The nano-porous SiO2 solids

with Pt or Pd metal nanoparticles were also used [171-172], and they offered higher electrooxidation current densities for both methanol and ethanol.

Novel Pt and Pd Based Core-Shell Catalysts with Critical New Issues of Heat Treatment, Stability and Durability for Proton Exchange Membrane Fuel Cells and Direct Methanol Fuel Cells 253

activity, PVP polymer of the as-prepared product of PVP-Pt nanoparticles was removed. Therefore, the pure Pt nanoparticles for electrochemical measurements can be obtained by using centrifuge. The resultant solution of as-prepared nanoparticle was washed by using the suitable mixtures of acetone and followed by centrifugation at 5,000 rpm up to 15,000 rpm. Next, the black solid product was re-dispersed in the ethanol/hexane mixtures with a suitable volume rate. The resultant mixture was centrifuged in order to obtain the fresh product. Experimentally, the procedures of washing and clean Pt nanoparticles in the mixture of ethanol and hexane were done many times. After washing PVP polymer and contaminations in the as-prepared product, the nanoparticles were dispersed in milli-Q water in order to achieve the fixed density of colloidal Pt nanoparticles at 1 mg/mL with the aid of ICPS analyzer. The working electrode was a glassy carbon rod (RA-5, Tokai Carbon Co., Ltd.) with a diameter of 5.2 mm. Then, the electrode surface was cleaned and activated by using a kind of polishing-cloth (Buehler Textmet) with alumina slurry (Aldrich, particle size of 50 nm), followed by washing any contaminations with milli-Q water. The step-bystep procedures were repeated until the surface looked like a mirror. Then, a fixed weight of some μg (e.g. 5 μg or 10 *μ*g) of the Pt loading was set onto the surface of the polished electrode for the electrochemical measurements. The loaded electrodes were dried in air for 3 h at 25 °C and heated with the heating rate of 1 °C/min up to 450 °C or 723 K in air and a keeping time of 2 h in order to remove organic species [128-130]. We used a very slow heating rate to avoid the serious problem of sintering of the pure nanoparticles so that the layer catalyst is the nanoparticles. The electrodes were allowed to cool normally and then exposed into the flow of the mixture of H2/N2 gases (20%,80%) at 100 °C for 3 h to reduce the existence of PtO and ensure a pristine catalyst surface. In order to improve the mechanical stability of electrode surfaces, Nafion® solution, e.g. 10 *μ*L of 5 wt.%, was added onto the electrode and followed by drying in air for a long time, e.g. overnight, before the electrochemical measurements. The cyclic voltammetry experiment was performed at room temperature using a typical setup of three-electrode electrochemical system in figure 5(h) connected to Potentiostat (SI-1287 Electrochemical Interface, Solartron). The cell was a 50 mL glass vial, which was carefully treated with the mixture of H2SO4 and HNO3, and then washed generously with milli-Q water. A leak-free AgCl/Ag/NaCl electrode (RE-1B,ALS) served as the reference and all the potentials were reported vs. Ag/AgCl. The counter electrode was a Pt coil (002234,ALS) [128-130, 140-143]. The electrolyte solution was bubbled with N2 gas for 30 min before every measurement. This N2 blanket was kept during the actual course of potential sweeping. For the base voltammetry, the electrolyte was a solution of 0.1 M HClO4 that was diluted from 70% concentrated solution (Aldrich) using milli-Q water. Additionally, 0.5 M H2SO4, H2SO4 and 1 M CH3OH are prepared for electrochemical measurements. The potential window between -0.2 to 1.0 V with a sweep rate of 50 mV/s was used. For the methanol oxidation, the electrolyte was added with 1.0 M methanol in milli-Q water. The system measurements were cycled until the stable voltammograms were achieved. The electrochemical surface area (ECA) or ECSA was estimated by considering the area under the curve in the hydrogen desorption region of the forward scan and using 0.21 mC/cm2 for the monolayer of hydrogen adsorbed on the surface of Pt catalyst [13,174]. The CO poisoning issues or phenomena of CO-stripping voltammetry of the Pt catalysts cause a

## **5.1. Heat treatment**

Before the TEM and HRTEM measurements, copper grids with the prepared nanoparticles were annealed in the heat treatment at 300 oC for 4 h, 6 h or even a half day. The evidences and results of the characterization of size, structure, shape, morphology with the only Pt composition by TEM and HRTEM show the uniform polyhedral Pt nanoparticles synthesized by polyol method with the controlled size in the nanosized range of 10 nm and 20 nm, and sharp shapes and morphologies through an introduction of low contents of AgNO3 as size, structure, morphology and shape-controlling reagent and the gradual addition of the precursors of PVP and H2PtCl6 in the suitable volume ratio. In the characterizations of homogeneous polyhedral morphology and shape, the appearances of the main sharp cubic, octahedral, and tetrahedral shapes of Pt NPs in the controlled growth of (100), (110), and (111) selective surfaces are very good for their applications in catalytic activity, e.g. the ORR and MOR chemical reactions because the polyhedral Pt nanoparticles have at a higher concentration of surface steps, kinks, islands, terraces, and corners [10- 12,188]. In addition, the TEM and HRTEM images of Pt NPs by polyol method show interestingly important phenomena of particle-particle surface attachment, self-aggregation, and assembly in the case of the use of the pure Pt NPs or the PVP-Pt NPs. Most of Pt NPs showed various large morphologies and shape after heat treatment at high temperature from 20 to 60 nm for the case of the PVP-Pt NPs [128-130]. The clear overgrowths and structural transformation in the nanosized range of polyhedral Pt nanoparticles annealed at 300 °C for 4 h were observed. Clearly, the morphology of PVP-Pt nanoparticles was significantly changed by heat treatment. During their synthesis, PVP polymer is used to stabilize and control the size and morphology of Pt nanoparticles against their aggregation. In addition, the amount of PVP polymer can bind the nanoparticle surface after the catalyst synthesis. Therefore, PVP or other polymers for the protections of the as-prepared nanoparticles should be removed in the minimal content before the catalytic reactions. In our research, PVP polymer plays an important role to stabilize their morphology and size of these Pt nanoparticles. Despite the fact that these Pt nanoparticles were put on copper grids, they still have their interfacial interactions to their particle-particle surface attachments, aggregation, and self-assembly leading to form the larger and irregular Pt particles or the larger particles in the forms of hetero-morphologies and hetero-nanostructures in the final formation by the heat treatment. It is known that Pt nanostructures with the issues of size, shape and morphology under heat treatment procedures become important to further investigation in the confirmation of catalytic activity in catalysis. The critical issues of size, shape and morphology of colloidal nanoparticles need to be intensively studied in different media (condense, liquid, and gas) for the certain confirmations of high and long-term stability, high durability, and safety in their practical applications in catalysis, biology and medicine. In our experimental methods, in order to obtain the pure Pt catalyst for the standard catalyst of the standard nanosized range of 10 nm in investigations of catalytic 252 Heat Treatment – Conventional and Novel Applications

**5.1. Heat treatment** 

oxidation current densities for both methanol and ethanol.

with Pt or Pd metal nanoparticles were also used [171-172], and they offered higher electro-

Before the TEM and HRTEM measurements, copper grids with the prepared nanoparticles were annealed in the heat treatment at 300 oC for 4 h, 6 h or even a half day. The evidences and results of the characterization of size, structure, shape, morphology with the only Pt composition by TEM and HRTEM show the uniform polyhedral Pt nanoparticles synthesized by polyol method with the controlled size in the nanosized range of 10 nm and 20 nm, and sharp shapes and morphologies through an introduction of low contents of AgNO3 as size, structure, morphology and shape-controlling reagent and the gradual addition of the precursors of PVP and H2PtCl6 in the suitable volume ratio. In the characterizations of homogeneous polyhedral morphology and shape, the appearances of the main sharp cubic, octahedral, and tetrahedral shapes of Pt NPs in the controlled growth of (100), (110), and (111) selective surfaces are very good for their applications in catalytic activity, e.g. the ORR and MOR chemical reactions because the polyhedral Pt nanoparticles have at a higher concentration of surface steps, kinks, islands, terraces, and corners [10- 12,188]. In addition, the TEM and HRTEM images of Pt NPs by polyol method show interestingly important phenomena of particle-particle surface attachment, self-aggregation, and assembly in the case of the use of the pure Pt NPs or the PVP-Pt NPs. Most of Pt NPs showed various large morphologies and shape after heat treatment at high temperature from 20 to 60 nm for the case of the PVP-Pt NPs [128-130]. The clear overgrowths and structural transformation in the nanosized range of polyhedral Pt nanoparticles annealed at 300 °C for 4 h were observed. Clearly, the morphology of PVP-Pt nanoparticles was significantly changed by heat treatment. During their synthesis, PVP polymer is used to stabilize and control the size and morphology of Pt nanoparticles against their aggregation. In addition, the amount of PVP polymer can bind the nanoparticle surface after the catalyst synthesis. Therefore, PVP or other polymers for the protections of the as-prepared nanoparticles should be removed in the minimal content before the catalytic reactions. In our research, PVP polymer plays an important role to stabilize their morphology and size of these Pt nanoparticles. Despite the fact that these Pt nanoparticles were put on copper grids, they still have their interfacial interactions to their particle-particle surface attachments, aggregation, and self-assembly leading to form the larger and irregular Pt particles or the larger particles in the forms of hetero-morphologies and hetero-nanostructures in the final formation by the heat treatment. It is known that Pt nanostructures with the issues of size, shape and morphology under heat treatment procedures become important to further investigation in the confirmation of catalytic activity in catalysis. The critical issues of size, shape and morphology of colloidal nanoparticles need to be intensively studied in different media (condense, liquid, and gas) for the certain confirmations of high and long-term stability, high durability, and safety in their practical applications in catalysis, biology and medicine. In our experimental methods, in order to obtain the pure Pt catalyst for the standard catalyst of the standard nanosized range of 10 nm in investigations of catalytic activity, PVP polymer of the as-prepared product of PVP-Pt nanoparticles was removed.

Therefore, the pure Pt nanoparticles for electrochemical measurements can be obtained by using centrifuge. The resultant solution of as-prepared nanoparticle was washed by using the suitable mixtures of acetone and followed by centrifugation at 5,000 rpm up to 15,000 rpm. Next, the black solid product was re-dispersed in the ethanol/hexane mixtures with a suitable volume rate. The resultant mixture was centrifuged in order to obtain the fresh product. Experimentally, the procedures of washing and clean Pt nanoparticles in the mixture of ethanol and hexane were done many times. After washing PVP polymer and contaminations in the as-prepared product, the nanoparticles were dispersed in milli-Q water in order to achieve the fixed density of colloidal Pt nanoparticles at 1 mg/mL with the aid of ICPS analyzer. The working electrode was a glassy carbon rod (RA-5, Tokai Carbon Co., Ltd.) with a diameter of 5.2 mm. Then, the electrode surface was cleaned and activated by using a kind of polishing-cloth (Buehler Textmet) with alumina slurry (Aldrich, particle size of 50 nm), followed by washing any contaminations with milli-Q water. The step-bystep procedures were repeated until the surface looked like a mirror. Then, a fixed weight of some μg (e.g. 5 μg or 10 *μ*g) of the Pt loading was set onto the surface of the polished electrode for the electrochemical measurements. The loaded electrodes were dried in air for 3 h at 25 °C and heated with the heating rate of 1 °C/min up to 450 °C or 723 K in air and a keeping time of 2 h in order to remove organic species [128-130]. We used a very slow heating rate to avoid the serious problem of sintering of the pure nanoparticles so that the layer catalyst is the nanoparticles. The electrodes were allowed to cool normally and then exposed into the flow of the mixture of H2/N2 gases (20%,80%) at 100 °C for 3 h to reduce the existence of PtO and ensure a pristine catalyst surface. In order to improve the mechanical stability of electrode surfaces, Nafion® solution, e.g. 10 *μ*L of 5 wt.%, was added onto the electrode and followed by drying in air for a long time, e.g. overnight, before the electrochemical measurements. The cyclic voltammetry experiment was performed at room temperature using a typical setup of three-electrode electrochemical system in figure 5(h) connected to Potentiostat (SI-1287 Electrochemical Interface, Solartron). The cell was a 50 mL glass vial, which was carefully treated with the mixture of H2SO4 and HNO3, and then washed generously with milli-Q water. A leak-free AgCl/Ag/NaCl electrode (RE-1B,ALS) served as the reference and all the potentials were reported vs. Ag/AgCl. The counter electrode was a Pt coil (002234,ALS) [128-130, 140-143]. The electrolyte solution was bubbled with N2 gas for 30 min before every measurement. This N2 blanket was kept during the actual course of potential sweeping. For the base voltammetry, the electrolyte was a solution of 0.1 M HClO4 that was diluted from 70% concentrated solution (Aldrich) using milli-Q water. Additionally, 0.5 M H2SO4, H2SO4 and 1 M CH3OH are prepared for electrochemical measurements. The potential window between -0.2 to 1.0 V with a sweep rate of 50 mV/s was used. For the methanol oxidation, the electrolyte was added with 1.0 M methanol in milli-Q water. The system measurements were cycled until the stable voltammograms were achieved. The electrochemical surface area (ECA) or ECSA was estimated by considering the area under the curve in the hydrogen desorption region of the forward scan and using 0.21 mC/cm2 for the monolayer of hydrogen adsorbed on the surface of Pt catalyst [13,174]. The CO poisoning issues or phenomena of CO-stripping voltammetry of the Pt catalysts cause a

#### 254 Heat Treatment – Conventional and Novel Applications

significant decrease in the overall efficiency of DMFCs. In all CV research, we did not observe CO poisoning in the CV data. The evidences proved that heat treatments are very important to engineer the best Pt catalyst or the better Pt based catalyst for FCs, PEMFCs, and DMFCs. In the developments of FCs, PEMFCs, DMFCs, novel Pt and Pd based coreshell bimetallic nanosystems or Pt and Pd core-shell catalysts will be the next catalysts with use of the thin Pt or Pt-Pd shells on the thick cores (metals, oxides, glasses, and ceramics) in the nanosized ranges of 10 nm, 20 nm and 30 nm. The thin Pt metal shells or Pt based noble bimetal (noble Pt-Pd, Pt-Ir, Pt-Ru, Pt-Rh, Pt-Au, Pt-Ag) thin shells can be tuned to be several nanometers on the metal or alloy cores in the ranges of 10 nm, 20 nm and 30 nm, and so on through the controlled synthesis and preparation processes. Unfortunately, quantum-size, structural and surface effects of metal nanoparticles around 10 nm in electro-catalysis are not fully understood in their chemical and structural changes.

Novel Pt and Pd Based Core-Shell Catalysts with Critical New Issues of Heat Treatment, Stability and Durability for Proton Exchange Membrane Fuel Cells and Direct Methanol Fuel Cells 255

polyhedral Pt nanoparticles under control in the size, shape and morphology in the nanosized range of 10 nm should be used the standard catalyst in the scientific investigations of catalysis for FCs, PEMFCs and DMFCs. Our electrochemical measurements were performed by the use of the pure Pt catalysts of polyhedral Pt nanoparticles or the Pt based catalysts in alloy and core-shell structure in the mixture of 0.1 M HClO4/1 M methanol (or 0.5 H2SO4/1 M methanol). In these CV measurements, the stable voltammograms are attained after about 10-20 cycles of sweeping between -0.2 to 1.0 V potential range. The typical two oxidation peaks are observed in the evidences of methanol oxidation. The first one is between 0.6 and 0.7 V in the forward scan, and the other at around 0.4 V and 0.5 V in the reverse scan [129]. The two peaks showed the good methanol oxidation and its associated intermediate species. Our results of methanol oxidation with the use of the pure Pt catalyst prepared are agreement with other scientific reports. The peak current density in the forward scan serves as benchmark for the catalytic activity of Pt nanoparticles during methanol dehydrogenation. For the prepared catalyst samples, its values are 7.62×10-4 A/cm2 (washed-only samples), 8.75×10-4 (heated-only samples), and 9.90×10-4 (washed and heated samples), respectively [129]. Therefore, the as-prepared Pt nanoparticles should be washed with organic solvents before heating them at a specific temperature. It is known that PVP can be polymer that only protects the as-prepared Pt nanoparticles in the solution products that seriously decrease the catalytic activity of Pt nanoparticles in MOR. Therefore, PVP or other polymers should be completely removed in the centrifugation processes by centrifuge systems for the pure Pt and Pd based catalyst before high heat treatments for to enhance catalytic activity of Pt nanoparticles for FCs, PEMFCs, and DMFCs, primarily towards

In the development and commercialization of various FCs, PEMFCs, and DMFCs, the next Pt and Pt based bimetal nanoparticles of internal structure, surface structure, shape and morphology in the nanosized ranges, typically 10 nm, 20 nm, and 30 nm are the best potential catalysts for a significant reduction of the very high costs of various FCs, PEMFCs, and DMFCs. The aim of this chapter is to demonstrate that the urgent demands of studying and synthesizing for the next Pt based catalysts of highly long-term stability and durability are crucial to create low-cost products of PEMFCs and DMFCs. The low cost of low and high temperature FCs, PEMFCs and DMFCs is an extremely important factor for large-scale commercialization. The low-cost Pt and Pd based catalysts can be the good solution to the big challenges of the costs of low and high temperature FCs, PEMFCs, and DMFCs. The modifications and improvements of the catalyst layer materials, and their synthesis become important factors. It should be stressed that next low and high temperature FCs for direct conversion from chemical energy into electrical energy will be very crucial to offer potential applications in portable power supply for mobile use or portable devices or transportation vehicles. Thus, large-efficiency FCs for direct energy conversion via chemical reaction into

methanol electro-oxidation (MOR) in DMFCs.

electricity can be commercially realized in near future.

**6. Prospects and conclusion** 

## **5.2. Stability and durability**

With respect to the heat treatment, electrocatalytic characterizations of the pure catalyst with our as-prepare products of Pt nanoparticles showed highly good quality, long-term stability and durability. Thus, the significant effects of time and temperature during heat treatment for the pure Pt catalyst or Pt/support catalysts are crucial. In our research, the findings and results involve in the cyclic voltammograms of polyhedral Pt nanoparticles with the different removal of PVP polymer acquired at 50 mV/s in 0.1 M HClO4 solution (or in 0.5 H2SO4 or in 0.5 H2SO4 and 1 M CH3OH). The voltammograms data proved the typical shape for the base voltammetry for the high activity, stability and durability of our catalysts used [98,99,129]. The very high activity, durability and stability in FCs described were achieved up to 200,000 cycles with the use of core-shell catalysts with the Pt-monolayers shells in the cathode as important scientific evidences [99]. In our interesting research, the structural effects of low and high-index planes of the fcc structure of Pt catalyst were confirmed in electrochemical measurements, typical low-index planes of (111), (110), and (100) or more high index planes (hkl). The Volmer-Tafel and Volmer-Heyrovsky mechanisms are observed in hydrogen reactions. Most of ORR evidences showed good oxygen reduction. Therefore, our results showed the important evidences of the catalytic activity of the Pt catalyst or Pt based catalysts with alloy structures or core-shell structures. The ECA of the Pt catalyst the use of the Pt nanoparticles washed and heated showed the best catalytic activity (ECA=10.53 m2/g), better than Pt catalyst the use of the Pt nanoparticles heated only-Pt nanoparticles (8.56 m2/g), and better than Pt catalyst the use of the Pt nanoparticles of washed-only Pt nanoparticles (6.75 m2/g). The values proved that the high stability and durability of the catalyst preparation, processes of heat treatment, methods of washing and clean the asprepared Pt nanoparticles for the pure Pt catalyst. However, we should find a good process of heat treatment to avoid particle sintering in the electrodes at high temperature more than 450 °C and keep the good characterizations of size, internal structure, surface structure, shape and morphology of the Pt nanoparticles or the Pt based nanoparticles for the pure Pt based catalysts for FCs, PEMFCs and DMFCs. Therefore, we propose that homogeneous polyhedral Pt nanoparticles under control in the size, shape and morphology in the nanosized range of 10 nm should be used the standard catalyst in the scientific investigations of catalysis for FCs, PEMFCs and DMFCs. Our electrochemical measurements were performed by the use of the pure Pt catalysts of polyhedral Pt nanoparticles or the Pt based catalysts in alloy and core-shell structure in the mixture of 0.1 M HClO4/1 M methanol (or 0.5 H2SO4/1 M methanol). In these CV measurements, the stable voltammograms are attained after about 10-20 cycles of sweeping between -0.2 to 1.0 V potential range. The typical two oxidation peaks are observed in the evidences of methanol oxidation. The first one is between 0.6 and 0.7 V in the forward scan, and the other at around 0.4 V and 0.5 V in the reverse scan [129]. The two peaks showed the good methanol oxidation and its associated intermediate species. Our results of methanol oxidation with the use of the pure Pt catalyst prepared are agreement with other scientific reports. The peak current density in the forward scan serves as benchmark for the catalytic activity of Pt nanoparticles during methanol dehydrogenation. For the prepared catalyst samples, its values are 7.62×10-4 A/cm2 (washed-only samples), 8.75×10-4 (heated-only samples), and 9.90×10-4 (washed and heated samples), respectively [129]. Therefore, the as-prepared Pt nanoparticles should be washed with organic solvents before heating them at a specific temperature. It is known that PVP can be polymer that only protects the as-prepared Pt nanoparticles in the solution products that seriously decrease the catalytic activity of Pt nanoparticles in MOR. Therefore, PVP or other polymers should be completely removed in the centrifugation processes by centrifuge systems for the pure Pt and Pd based catalyst before high heat treatments for to enhance catalytic activity of Pt nanoparticles for FCs, PEMFCs, and DMFCs, primarily towards methanol electro-oxidation (MOR) in DMFCs.

## **6. Prospects and conclusion**

254 Heat Treatment – Conventional and Novel Applications

**5.2. Stability and durability** 

not fully understood in their chemical and structural changes.

significant decrease in the overall efficiency of DMFCs. In all CV research, we did not observe CO poisoning in the CV data. The evidences proved that heat treatments are very important to engineer the best Pt catalyst or the better Pt based catalyst for FCs, PEMFCs, and DMFCs. In the developments of FCs, PEMFCs, DMFCs, novel Pt and Pd based coreshell bimetallic nanosystems or Pt and Pd core-shell catalysts will be the next catalysts with use of the thin Pt or Pt-Pd shells on the thick cores (metals, oxides, glasses, and ceramics) in the nanosized ranges of 10 nm, 20 nm and 30 nm. The thin Pt metal shells or Pt based noble bimetal (noble Pt-Pd, Pt-Ir, Pt-Ru, Pt-Rh, Pt-Au, Pt-Ag) thin shells can be tuned to be several nanometers on the metal or alloy cores in the ranges of 10 nm, 20 nm and 30 nm, and so on through the controlled synthesis and preparation processes. Unfortunately, quantum-size, structural and surface effects of metal nanoparticles around 10 nm in electro-catalysis are

With respect to the heat treatment, electrocatalytic characterizations of the pure catalyst with our as-prepare products of Pt nanoparticles showed highly good quality, long-term stability and durability. Thus, the significant effects of time and temperature during heat treatment for the pure Pt catalyst or Pt/support catalysts are crucial. In our research, the findings and results involve in the cyclic voltammograms of polyhedral Pt nanoparticles with the different removal of PVP polymer acquired at 50 mV/s in 0.1 M HClO4 solution (or in 0.5 H2SO4 or in 0.5 H2SO4 and 1 M CH3OH). The voltammograms data proved the typical shape for the base voltammetry for the high activity, stability and durability of our catalysts used [98,99,129]. The very high activity, durability and stability in FCs described were achieved up to 200,000 cycles with the use of core-shell catalysts with the Pt-monolayers shells in the cathode as important scientific evidences [99]. In our interesting research, the structural effects of low and high-index planes of the fcc structure of Pt catalyst were confirmed in electrochemical measurements, typical low-index planes of (111), (110), and (100) or more high index planes (hkl). The Volmer-Tafel and Volmer-Heyrovsky mechanisms are observed in hydrogen reactions. Most of ORR evidences showed good oxygen reduction. Therefore, our results showed the important evidences of the catalytic activity of the Pt catalyst or Pt based catalysts with alloy structures or core-shell structures. The ECA of the Pt catalyst the use of the Pt nanoparticles washed and heated showed the best catalytic activity (ECA=10.53 m2/g), better than Pt catalyst the use of the Pt nanoparticles heated only-Pt nanoparticles (8.56 m2/g), and better than Pt catalyst the use of the Pt nanoparticles of washed-only Pt nanoparticles (6.75 m2/g). The values proved that the high stability and durability of the catalyst preparation, processes of heat treatment, methods of washing and clean the asprepared Pt nanoparticles for the pure Pt catalyst. However, we should find a good process of heat treatment to avoid particle sintering in the electrodes at high temperature more than 450 °C and keep the good characterizations of size, internal structure, surface structure, shape and morphology of the Pt nanoparticles or the Pt based nanoparticles for the pure Pt based catalysts for FCs, PEMFCs and DMFCs. Therefore, we propose that homogeneous

In the development and commercialization of various FCs, PEMFCs, and DMFCs, the next Pt and Pt based bimetal nanoparticles of internal structure, surface structure, shape and morphology in the nanosized ranges, typically 10 nm, 20 nm, and 30 nm are the best potential catalysts for a significant reduction of the very high costs of various FCs, PEMFCs, and DMFCs. The aim of this chapter is to demonstrate that the urgent demands of studying and synthesizing for the next Pt based catalysts of highly long-term stability and durability are crucial to create low-cost products of PEMFCs and DMFCs. The low cost of low and high temperature FCs, PEMFCs and DMFCs is an extremely important factor for large-scale commercialization. The low-cost Pt and Pd based catalysts can be the good solution to the big challenges of the costs of low and high temperature FCs, PEMFCs, and DMFCs. The modifications and improvements of the catalyst layer materials, and their synthesis become important factors. It should be stressed that next low and high temperature FCs for direct conversion from chemical energy into electrical energy will be very crucial to offer potential applications in portable power supply for mobile use or portable devices or transportation vehicles. Thus, large-efficiency FCs for direct energy conversion via chemical reaction into electricity can be commercially realized in near future.
