35. Fontecilla-Camps JC, Volbeda A, Cavazza C, Nicolet Y (2007) Structure/function relationships of [NiFe]- and [FeFe]-hydrogenases. Chem Rev 107(10):4273–4303
36. Fontecilla-Camps JC, Amara P, Cavazza C, Nicolet Y, Volbeda A (2009) Structure-function
relationships of anaerobic gas-processing metalloenzymes. Nature 460(7257):814–822
37. Adams MWW (1990) The structure and mechanism of iron-hydrogenases. Biochim Biophys
Acta (BBA) Bioenergetics 1020(2):115–145
38. Frey M (2002) Hydrogenases: hydrogen-activating enzymes. Chembiochem 3(2–3):153–160
39. Schilter D, Camara JM, Huynh MT, Hammes-Schiffer S, Rauchfuss TB (2016) Hydrogenase
enzymes and their synthetic models: the role of metal hydrides. Chem Rev 116(15):8693–8749
40. Zhang B, Sun L (2019) Artificial photosynthesis: opportunities and challenges of molecular
catalysts. Chem Soc Rev 48(7):2216–2264
41. Sakai K, Ozawa H (2007) Homogeneous catalysis of platinum(II) complexes in photochemical
hydrogen production from water. Coord Chem Rev 251(21–24):2753–2766
42. Fukuzumi S, Yamada Y, Suenobu T, Ohkubo K, Kotani H (2011) Catalytic mechanisms of
hydrogen evolution with homogeneous and heterogeneous catalysts. Energy Environ Sci 4(8)
43. Ogata H, Hirota S, Nakahara A, Komori H, Shibata N, Kato T, Kano K, Higuchi Y (2005)
Activation process of [NiFe] hydrogenase elucidated by high-resolution X-ray analyses:
conversion of the ready to the unready state. Structure 13(11):1635–1642
44. Nicolet Y, Piras C, Legrand P, Hatchikian CE, Fontecilla-Camps JC (1999) Desulfovibrio
desulfuricans iron hydrogenase: the structure shows unusual coordination to an active site Fe
binuclear center. Structure 7(1):13–23
45. Hiromoto T, Warkentin E, Moll J, Ermler U, Shima S (2009) The crystal structure of an [Fe]hydrogenase-substrate complex reveals the framework for H2 activation. Angew Chem Int Ed
Engl 48(35):6457–6460
46. Dempsey JL, Brunschwig BS, Winkler JR, Gray HB (2009) Hydrogen evolution catalyzed by
cobaloximes. Acc Chem Res 42(12):1995–2004
47. Artero V, Chavarot-Kerlidou M, Fontecave M (2011) Splitting water with cobalt. Angew
Chem Int Ed Engl 50(32):7238–7266
48. Losse S, Vos JG, Rau S (2010) Catalytic hydrogen production at cobalt centres. Coord Chem
Rev 254(21–22):2492–2504
49. Zhang P, Wang M, Gloaguen F, Chen L, Quentel F, Sun L (2013) Electrocatalytic hydrogen
evolution from neutral water by molecular cobalt tripyridine-diamine complexes. Chem
Commun (Camb) 49(82):9455–9457
50. Stubbert BD, Peters JC, Gray HB (2011) Rapid water reduction to H2 catalyzed by a cobalt bis
(iminopyridine) complex. J Am Chem Soc 133(45):18070–18073
51. Marinescu SC, Winkler JR, Gray HB (2012) Molecular mechanisms of cobalt-catalyzed
hydrogen evolution. Proc Natl Acad Sci U S A 109(38):15127–15131
52. Du P, Schneider J, Luo G, Brennessel WW, Eisenberg R (2009) Visible light-driven hydrogen
production from aqueous protons catalyzed by molecular cobaloxime catalysts. Inorg Chem 48
(11):4952–4962
53. Rakowski DuBois M, DuBois DL (2009) The roles of the first and second coordination
spheres in the design of molecular catalysts for H2 production and oxidation. Chem Soc
Rev 38(1):62–72
54. Rakowski DuBois M, DuBois DL (2009) Development of molecular electrocatalysts for CO2
reduction and H2 production/oxidation. Acc Chem Res 42(12):1974–1982
55. Wang M, Chen L, Sun L (2012) Recent progress in electrochemical hydrogen production with
earth-abundant metal complexes as catalysts. Energy Environ Sci 5(5)
56. Jacques PA, Artero V, Pecaut J, Fontecave M (2009) Cobalt and nickel diimine-dioxime
complexes as molecular electrocatalysts for hydrogen evolution with low overvoltages. Proc
Natl Acad Sci U S A 106(49):20627–20632
57. Le Goff A, Artero V, Jousselme B, Tran PD, Guillet N, Metaye R, Fihri A, Palacin S,
Fontecave M (2009) From hydrogenases to noble metal-free catalytic nanomaterials for H2
production and uptake. Science 326(5958):1384–1387
438
H.-T. Zhang and M.-T. Zhang
36. Fontecilla-Camps JC, Amara P, Cavazza C, Nicolet Y, Volbeda A (2009) Structure-function
relationships of anaerobic gas-processing metalloenzymes. Nature 460(7257):814–822
37. Adams MWW (1990) The structure and mechanism of iron-hydrogenases. Biochim Biophys
Acta (BBA) Bioenergetics 1020(2):115–145
38. Frey M (2002) Hydrogenases: hydrogen-activating enzymes. Chembiochem 3(2–3):153–160
39. Schilter D, Camara JM, Huynh MT, Hammes-Schiffer S, Rauchfuss TB (2016) Hydrogenase
enzymes and their synthetic models: the role of metal hydrides. Chem Rev 116(15):8693–8749
40. Zhang B, Sun L (2019) Artificial photosynthesis: opportunities and challenges of molecular
catalysts. Chem Soc Rev 48(7):2216–2264
41. Sakai K, Ozawa H (2007) Homogeneous catalysis of platinum(II) complexes in photochemical
hydrogen production from water. Coord Chem Rev 251(21–24):2753–2766
42. Fukuzumi S, Yamada Y, Suenobu T, Ohkubo K, Kotani H (2011) Catalytic mechanisms of
hydrogen evolution with homogeneous and heterogeneous catalysts. Energy Environ Sci 4(8)
43. Ogata H, Hirota S, Nakahara A, Komori H, Shibata N, Kato T, Kano K, Higuchi Y (2005)
Activation process of [NiFe] hydrogenase elucidated by high-resolution X-ray analyses:
conversion of the ready to the unready state. Structure 13(11):1635–1642
44. Nicolet Y, Piras C, Legrand P, Hatchikian CE, Fontecilla-Camps JC (1999) Desulfovibrio
desulfuricans iron hydrogenase: the structure shows unusual coordination to an active site Fe
binuclear center. Structure 7(1):13–23
45. Hiromoto T, Warkentin E, Moll J, Ermler U, Shima S (2009) The crystal structure of an [Fe]hydrogenase-substrate complex reveals the framework for H2 activation. Angew Chem Int Ed
Engl 48(35):6457–6460
46. Dempsey JL, Brunschwig BS, Winkler JR, Gray HB (2009) Hydrogen evolution catalyzed by
cobaloximes. Acc Chem Res 42(12):1995–2004
47. Artero V, Chavarot-Kerlidou M, Fontecave M (2011) Splitting water with cobalt. Angew
Chem Int Ed Engl 50(32):7238–7266
48. Losse S, Vos JG, Rau S (2010) Catalytic hydrogen production at cobalt centres. Coord Chem
Rev 254(21–22):2492–2504
49. Zhang P, Wang M, Gloaguen F, Chen L, Quentel F, Sun L (2013) Electrocatalytic hydrogen
evolution from neutral water by molecular cobalt tripyridine-diamine complexes. Chem
Commun (Camb) 49(82):9455–9457
50. Stubbert BD, Peters JC, Gray HB (2011) Rapid water reduction to H2 catalyzed by a cobalt bis
(iminopyridine) complex. J Am Chem Soc 133(45):18070–18073
51. Marinescu SC, Winkler JR, Gray HB (2012) Molecular mechanisms of cobalt-catalyzed
hydrogen evolution. Proc Natl Acad Sci U S A 109(38):15127–15131
52. Du P, Schneider J, Luo G, Brennessel WW, Eisenberg R (2009) Visible light-driven hydrogen
production from aqueous protons catalyzed by molecular cobaloxime catalysts. Inorg Chem 48
(11):4952–4962
53. Rakowski DuBois M, DuBois DL (2009) The roles of the first and second coordination
spheres in the design of molecular catalysts for H2 production and oxidation. Chem Soc
Rev 38(1):62–72
54. Rakowski DuBois M, DuBois DL (2009) Development of molecular electrocatalysts for CO2
reduction and H2 production/oxidation. Acc Chem Res 42(12):1974–1982
55. Wang M, Chen L, Sun L (2012) Recent progress in electrochemical hydrogen production with
earth-abundant metal complexes as catalysts. Energy Environ Sci 5(5)
56. Jacques PA, Artero V, Pecaut J, Fontecave M (2009) Cobalt and nickel diimine-dioxime
complexes as molecular electrocatalysts for hydrogen evolution with low overvoltages. Proc
Natl Acad Sci U S A 106(49):20627–20632
57. Le Goff A, Artero V, Jousselme B, Tran PD, Guillet N, Metaye R, Fihri A, Palacin S,
Fontecave M (2009) From hydrogenases to noble metal-free catalytic nanomaterials for H2
production and uptake. Science 326(5958):1384–1387
438
H.-T. Zhang and M.-T. Zhang