31. Armstrong FA, Belsey NA. Cracknell JA, Goldet G, Parkin A, Reisner E, Vincent KA,
Wait AF (2009) Dynamic electrochemical investigations of hydrogen oxidation and
production by enzymes and implications for future technology. Chem Soc Rev 38:36–51
32. Vincent K, Parkin A, Armstrong FA (2007) Investigating and exploiting the electrocatalytic
properties of hydrogenases. Chem Rev 107:4366–4413
33. Hexter SV, Chung MW, Vincent KA, Armstrong FA (2014) Unusual reaction of
NiFe-hydrogenases with cyanide. J Am Chem Soc 136:10470–10477
34. Fourmond V, Lautier T, Baffert C, Leroux F, Liebgott PP, Dementin S, Rousset M,
Arnoux P, Pignol D, Meynial-Salles I, Soucaille P, Bertrand P, Leger C (2009) Correcting
for electrocatalyst desorption and inactivation in chronoamperometry experiments. Anal
Chem 81:2962–2968
35. Krassen H, Stripp S, von Abendroth G, Ataka K, Happe T, Heberle J (2009) Immobilization
of the [FeFe]-hydrogenase CrHydA1 on a gold electrode: design of a catalytic surface for the
production of molecular hydrogen. J Biotechnol 142:3–9
36. Kihara T, Liu XY, Nakamura C, Park KM, Han SW, Qian DJ, Kawasaki K, Zorin NA,
Yasuda S, Hata K, Wakayama T, Miyake J (2011) Direct electron transfer to hydrogenase
for catalytic hydrogen production using a single-walled carbon nanotube forest. Int J
Hydrogen Energy 36:7523–7529
37. Morra S, Valetti F, Sarasso V, Castrignano S, Sadeghi SJ, Gilardi G (2015) Hydrogen
production at high faradaic efficiency by a bio-electrode based on TiO2 adsorption of a new
FeFe-hydrogenase from Clostridium perfringens. Bioelectrochemistry 106:258–262
38. Schlicht S, Assaud L, Hansen M, Licklederer M, Bechelany M, Perner M, Bachmann J
(2016) An electrochemically functional layer of hydrogenase extract on an electrode of large
and tunable specific surface area. J Mater Chem A 4:6487–6494
39. Shiraiwa S, So K, Sugimoto Y, Kitazumi Y, Shirai O, Nishikawa K, Higuchi Y, Kano K
(2018) Reactivation of standard [NiFe]-hydrogenase and bioelectrochemical catalysis of
proton reduction and hydrogen oxidation in a mediated-electron-transfer system. Bioelectrochemistry 123:156–161
40. Wakerley DW, Reisner E (2015) Oxygen tolerant proton reduction catalysis: much O 2 about
nothing. Energy Environ Sci 8:2283–2295
41. Gutiérrez-Sanz O, Tapia C, Marques MC, Zacarías S, Vélez M, Pereira IAC, De Lacey AL
(2015) Induction of a proton gradient across a gold-supported biomimetic membrane by
electroenzymatic H 2 oxidation. Angew Chem Int Ed 54:2684–2687
42. Rodriguez-Macia P, Birrell J, Lubitz W, Rüdiger O (2017) Electrochemical investigations on
the inactivation of the [FeFe] hydrogenase from Desulfovibrio desulfuricans by O 2 or light
under hydrogen-producing conditions. ChemPlusChem 82:540–545
43. Caserta G, Papini C, Adamska-Venkatesh A, Pecqueur L, Sommer C, Reijerse E, Lubitz W,
Gauquelin C, Meynial-Salles I, Pramanik D, Artero V, Atta M, del Barrio M, Faivre B,
Fourmond V, Leger C, Fontecave M (2018) Engineering an FeFe-hydrogenase: do accessory
clusters influence O 2 resistance and catalytic bias? J Am Chem Soc 140:5516–5526
44. Reisner E, Fontecilla-Camps JC, Armstrong FA (2009) Catalytic electrochemistry of a
[NiFeSe]-hydrogenase on TiO 2 and demonstration of its suitability for visible-light driven
H 2 production. Chem Commun 550–552
45. Reisner E, Powell DJ, Cavazza C, Fontecilla-Camps JC, Armstrong FA (2009) Visible
light-driven h 2 production by hydrogenases attached to dye-sensitized TiO 2 nanoparticles.
J Am Chem Soc 131:18457–18466
46. Brown KA, Dayal S, Ai X, Rumbles G, King PW (2010) Controlled assembly of
hydrogenase-CdTe nanocrystal hybrids for solar hydrogen production. J Am Chem Soc
132:9672–9680
47. Greene BL, Joseph CA, Maroney MJ, Dyer RB (2012) Direct evidence of active-site
reduction and photodriven catalysis in sensitized hydrogenase assemblies. J Am Chem Soc
134:11108–11111
268
M. Martins et al.
Wait AF (2009) Dynamic electrochemical investigations of hydrogen oxidation and
production by enzymes and implications for future technology. Chem Soc Rev 38:36–51
32. Vincent K, Parkin A, Armstrong FA (2007) Investigating and exploiting the electrocatalytic
properties of hydrogenases. Chem Rev 107:4366–4413
33. Hexter SV, Chung MW, Vincent KA, Armstrong FA (2014) Unusual reaction of
NiFe-hydrogenases with cyanide. J Am Chem Soc 136:10470–10477
34. Fourmond V, Lautier T, Baffert C, Leroux F, Liebgott PP, Dementin S, Rousset M,
Arnoux P, Pignol D, Meynial-Salles I, Soucaille P, Bertrand P, Leger C (2009) Correcting
for electrocatalyst desorption and inactivation in chronoamperometry experiments. Anal
Chem 81:2962–2968
35. Krassen H, Stripp S, von Abendroth G, Ataka K, Happe T, Heberle J (2009) Immobilization
of the [FeFe]-hydrogenase CrHydA1 on a gold electrode: design of a catalytic surface for the
production of molecular hydrogen. J Biotechnol 142:3–9
36. Kihara T, Liu XY, Nakamura C, Park KM, Han SW, Qian DJ, Kawasaki K, Zorin NA,
Yasuda S, Hata K, Wakayama T, Miyake J (2011) Direct electron transfer to hydrogenase
for catalytic hydrogen production using a single-walled carbon nanotube forest. Int J
Hydrogen Energy 36:7523–7529
37. Morra S, Valetti F, Sarasso V, Castrignano S, Sadeghi SJ, Gilardi G (2015) Hydrogen
production at high faradaic efficiency by a bio-electrode based on TiO2 adsorption of a new
FeFe-hydrogenase from Clostridium perfringens. Bioelectrochemistry 106:258–262
38. Schlicht S, Assaud L, Hansen M, Licklederer M, Bechelany M, Perner M, Bachmann J
(2016) An electrochemically functional layer of hydrogenase extract on an electrode of large
and tunable specific surface area. J Mater Chem A 4:6487–6494
39. Shiraiwa S, So K, Sugimoto Y, Kitazumi Y, Shirai O, Nishikawa K, Higuchi Y, Kano K
(2018) Reactivation of standard [NiFe]-hydrogenase and bioelectrochemical catalysis of
proton reduction and hydrogen oxidation in a mediated-electron-transfer system. Bioelectrochemistry 123:156–161
40. Wakerley DW, Reisner E (2015) Oxygen tolerant proton reduction catalysis: much O 2 about
nothing. Energy Environ Sci 8:2283–2295
41. Gutiérrez-Sanz O, Tapia C, Marques MC, Zacarías S, Vélez M, Pereira IAC, De Lacey AL
(2015) Induction of a proton gradient across a gold-supported biomimetic membrane by
electroenzymatic H 2 oxidation. Angew Chem Int Ed 54:2684–2687
42. Rodriguez-Macia P, Birrell J, Lubitz W, Rüdiger O (2017) Electrochemical investigations on
the inactivation of the [FeFe] hydrogenase from Desulfovibrio desulfuricans by O 2 or light
under hydrogen-producing conditions. ChemPlusChem 82:540–545
43. Caserta G, Papini C, Adamska-Venkatesh A, Pecqueur L, Sommer C, Reijerse E, Lubitz W,
Gauquelin C, Meynial-Salles I, Pramanik D, Artero V, Atta M, del Barrio M, Faivre B,
Fourmond V, Leger C, Fontecave M (2018) Engineering an FeFe-hydrogenase: do accessory
clusters influence O 2 resistance and catalytic bias? J Am Chem Soc 140:5516–5526
44. Reisner E, Fontecilla-Camps JC, Armstrong FA (2009) Catalytic electrochemistry of a
[NiFeSe]-hydrogenase on TiO 2 and demonstration of its suitability for visible-light driven
H 2 production. Chem Commun 550–552
45. Reisner E, Powell DJ, Cavazza C, Fontecilla-Camps JC, Armstrong FA (2009) Visible
light-driven h 2 production by hydrogenases attached to dye-sensitized TiO 2 nanoparticles.
J Am Chem Soc 131:18457–18466
46. Brown KA, Dayal S, Ai X, Rumbles G, King PW (2010) Controlled assembly of
hydrogenase-CdTe nanocrystal hybrids for solar hydrogen production. J Am Chem Soc
132:9672–9680
47. Greene BL, Joseph CA, Maroney MJ, Dyer RB (2012) Direct evidence of active-site
reduction and photodriven catalysis in sensitized hydrogenase assemblies. J Am Chem Soc
134:11108–11111
268
M. Martins et al.