**Acknowledgements**

full recovery of OCV. It is of relevant interest to overcome hydrogenase inactivation in

As reviewed in this chapter, many of the CNTs based technologies are promising for the de‐ velopment of a green hydrogen economy. Not only abiotic dihydrogen storage, but also mi‐ crobial dihydrogen production and use of this green dihydrogen in biofuel cells can take advantages of the outstanding properties of CNTs. In all these applications, CNTs appear to play multiple roles including increase in surface area, increase in electron transfer rate, in‐ crease in directly connected enzymes. Possible protection against oxygen damage of en‐ zymes has even been strongly suggested. Use of CNTs thus allows to architecture threedimensional nanostructured interfaces which can be an alternative to strictly orientated proteins or enzymes for high direct electron transfer interfacial processes. The ease in ob‐ taining tuned surface functionalizations is one of the very attracting points in view of the

This is in particular the case for biofuel cells using dihydrogen as a fuel. During the last years, tremendous research on hydrogenase, the key enzyme for dihydrogen conversion, has led to the discovery, then control of some hydrogenases presenting properties that allow their use in biotechnological devices. During this year, based on these new resistant enzymes and on improved knowledge of how CNTs can enhance direct current densities, two H2/O2 biofuel cells have been reported. Although these biofuel cells constitute the first device using hydro‐ genases, they already deliver sufficient power density for small portable applications. No

However, various directions might be followed to further improve the biological system in such a way it could be commercially available. One is the enhancement of long-term stabili‐ ty of the device, which is obviously the critical point shared by (bio)fuel cells, yet. Search for more stable enzymes in the biodiversity or enzyme engineering has to be explored. Protec‐ tion of enzymes by various encapsulation procedures could be another solution given effi‐ cient interfacial electron transfer can be reached. The use of whole microorganisms with controlled and driven metabolism, or at least immobilization of naturally encapsulated en‐ zymes will be a next step. As an example, reconstitution of proteoliposomes with a mem‐ brane-bound hydrogenase was proved to enhance the stability of the enzyme [137]. This could be a novel route for preserving enzymes in their physiological environment, hence en‐ hancing their stability. New enzymes, with outstanding properties (T°, pH, inhibitors, sub‐ strate affinity…) have to be discovered and studied. Notably, two very recent publications report on a new thermostable bilirubin oxidase and a tyrosinase which present outstanding resistances to serum constituents [138, 139]. These two new enzymes appear to be able to efficiently replace the currently used BOD for implantable applications of biofuel cells.

More sophisticated materials interfaces, constituted of mixtures of CNTs with other con‐ ducting materials could bring a hierarchical porosity necessary for both enzyme immobiliza‐

doubt that this research field will gain more and more interest in a next future.

H2/O2 biofuel cell.

**10. Future directions**

454 Syntheses and Applications of Carbon Nanotubes and Their Composites

development of efficient bioelectrodes.

We gratefully acknowledge the contribution of Marielle Bauzan (Fermentation Plant Unit, IMM, CNRS, Marseille, France) for growing the bacteria, Dr Marianne Guiral, Dr Marianne Ilbert and Pascale Infossi for fruitful discussions. This work was supported by research grants from CNRS, Région PACA and ANR.
