101. Shaw WJ, Helm ML, DuBois DL (2013) A modular, energy-based approach to the development of nickel containing molecular electrocatalysts for hydrogen production and oxidation.
Bioenergetics 1827(8–9):1123–1139. doi:10.1016/j.bbabio.2013.01.003
102. Kilgore UJ, Roberts JAS, Pool DH, Appel AM, Stewart MP, DuBois MR, Dougherty WG,
Kassel WS, Bullock RM, DuBois DL (2011) [Ni(PPh 2 NC 6 H 4 X 2 ) 2 ]
2+ complexes as
electrocatalysts for H 2 production: effect of substituents, acids, and water on catalytic rates.
J Am Chem Soc 133(15):5861–5872. doi:10.1021/ja109755f
103. Kilgore UJ, Stewart MP, Helm ML, Dougherty WG, Kassel WS, DuBois MR, DuBois DL,
Bullock RM (2011) Studies of a series of [Ni(Pr 2 NPh 2 ) 2 (CH 3 CN)]
2+ complexes as
electrocatalysts for H 2 production: substituent variation at the phosphorous atom of the
P 2 N 2 ligand. Inorg Chem 50(21):10908–10918. doi:10.1021/ic201461a
104. DuBois DL, Bullock RM (2011) Molecular electrocatalysts for the oxidation of hydrogen and
the production of hydrogen - the role of pendant amines as proton relays. Eur J Inorg Chem
2011(7):1017–1027. doi:10.1002/ejic.201001081
105. O’Hagan M, Shaw WJ, Raugei S, Chen S (2011) Moving protons with pendant amines:
proton mobility in a nickel catalyst for oxidation of hydrogen. J Am Chem Soc 133
(36):14301–14312. doi:10.1021/ja201838x
106. Helm ML, Stewart MP, Bullock RM, DuBois MR, DuBois DL (2011) A synthetic nickel
electrocatalyst with a turnover frequency above 100,000 s
À1 for H 2 production. Science 333
(6044):863–866. doi:10.1126/science.1205864
107. Pool DH, Stewart MP, O’Hagan M, Shaw WJ, Roberts JAS, Bullock RM, DuBois DL (2012)
Acidic ionic liquid/water solution as both medium and proton source for electrocatalytic H 2
evolution by [Ni(P 2 N 2 ) 2 ]
2+ complexes. Proc Natl Acad Sci U S A 109(39):15634–15639.
doi:10.1073/pnas.1120208109
108. Hoffert WA, Roberts JAS, Bullock RM, Helm ML (2013) Production of H 2 at fast rates using
a nickel electrocatalyst in water–acetonitrile solutions. Chem Commun 49(71):7767–7769.
doi:10.1039/C3CC43203C
109. Das AK, Engelhard MH, Bullock RM (2014) A hydrogen-evolving Ni(P2N2)2
electrocatalyst covalently attached to a glassy carbon electrode: preparation, characterization,
and catalysis. Comparisons with the homogeneous analogue. Inorg Chem 53(13):6875–6885.
doi:10.1021/ic500701a
110. Tran PD, Le Goff A, Heidkamp J, Jousselme B, Guillet N, Palacin S, Dau H, Fontecave M,
Artero V (2011) Noncovalent modification of carbon nanotubes with pyrene-functionalized
nickel complexes: carbon monoxide tolerant catalysts for hydrogen evolution and uptake.
Angew Chem Int Ed 50(6):1371–1374. doi:10.1002/anie.201005427
111. 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 H 2
production and uptake. Science 326(5958):1384–1387. doi:10.1126/science.1179773
112. Dutta A, Lense S, Hou J, Engelhard MH, Roberts JAS, Shaw WJ (2013) Minimal proton
channel enables H 2 oxidation and production with a water-soluble nickel-based catalyst.
J Am Chem Soc 135(49):18490–18496. doi:10.1021/ja407826d
113. Ginovska-Pangovska B, Dutta A, Reback ML, Linehan JC, Shaw WJ (2014) Beyond the
active site: the impact of the outer coordination sphere on electrocatalysts for hydrogen
production and oxidation. Acc Chem Res 47(8):2621–2630. doi:10.1021/ar5001742
114. Dutta A, Roberts JAS, Shaw WJ (2014) Arginine-containing ligands enhance H2 oxidation
catalyst performance. Angew Chem Int Ed Engl 53(25):6487–6491. doi:10.1002/anie.
201402304
115. Dutta A, DuBois DL, Roberts JAS, Shaw WJ (2014) Amino acid modified Ni catalyst
exhibits reversible H 2 oxidation/production over a broad pH range at elevated temperatures.
Proc Natl Acad Sci U S A 111(46):16286–16291. doi:10.1073/pnas.1416381111
116. Yang Y, Wang M, Xue L, Zhang F, Chen L, Ahlquist MSG, Sun L (2014) Nickel complex
with internal bases as efficient molecular catalyst for photochemical H 2 production.
ChemSusChem 7(10):2889–2897. doi:10.1002/cssc.201402381
268
L. Gan et al.
Bioenergetics 1827(8–9):1123–1139. doi:10.1016/j.bbabio.2013.01.003
102. Kilgore UJ, Roberts JAS, Pool DH, Appel AM, Stewart MP, DuBois MR, Dougherty WG,
Kassel WS, Bullock RM, DuBois DL (2011) [Ni(PPh 2 NC 6 H 4 X 2 ) 2 ]
2+ complexes as
electrocatalysts for H 2 production: effect of substituents, acids, and water on catalytic rates.
J Am Chem Soc 133(15):5861–5872. doi:10.1021/ja109755f
103. Kilgore UJ, Stewart MP, Helm ML, Dougherty WG, Kassel WS, DuBois MR, DuBois DL,
Bullock RM (2011) Studies of a series of [Ni(Pr 2 NPh 2 ) 2 (CH 3 CN)]
2+ complexes as
electrocatalysts for H 2 production: substituent variation at the phosphorous atom of the
P 2 N 2 ligand. Inorg Chem 50(21):10908–10918. doi:10.1021/ic201461a
104. DuBois DL, Bullock RM (2011) Molecular electrocatalysts for the oxidation of hydrogen and
the production of hydrogen - the role of pendant amines as proton relays. Eur J Inorg Chem
2011(7):1017–1027. doi:10.1002/ejic.201001081
105. O’Hagan M, Shaw WJ, Raugei S, Chen S (2011) Moving protons with pendant amines:
proton mobility in a nickel catalyst for oxidation of hydrogen. J Am Chem Soc 133
(36):14301–14312. doi:10.1021/ja201838x
106. Helm ML, Stewart MP, Bullock RM, DuBois MR, DuBois DL (2011) A synthetic nickel
electrocatalyst with a turnover frequency above 100,000 s
À1 for H 2 production. Science 333
(6044):863–866. doi:10.1126/science.1205864
107. Pool DH, Stewart MP, O’Hagan M, Shaw WJ, Roberts JAS, Bullock RM, DuBois DL (2012)
Acidic ionic liquid/water solution as both medium and proton source for electrocatalytic H 2
evolution by [Ni(P 2 N 2 ) 2 ]
2+ complexes. Proc Natl Acad Sci U S A 109(39):15634–15639.
doi:10.1073/pnas.1120208109
108. Hoffert WA, Roberts JAS, Bullock RM, Helm ML (2013) Production of H 2 at fast rates using
a nickel electrocatalyst in water–acetonitrile solutions. Chem Commun 49(71):7767–7769.
doi:10.1039/C3CC43203C
109. Das AK, Engelhard MH, Bullock RM (2014) A hydrogen-evolving Ni(P2N2)2
electrocatalyst covalently attached to a glassy carbon electrode: preparation, characterization,
and catalysis. Comparisons with the homogeneous analogue. Inorg Chem 53(13):6875–6885.
doi:10.1021/ic500701a
110. Tran PD, Le Goff A, Heidkamp J, Jousselme B, Guillet N, Palacin S, Dau H, Fontecave M,
Artero V (2011) Noncovalent modification of carbon nanotubes with pyrene-functionalized
nickel complexes: carbon monoxide tolerant catalysts for hydrogen evolution and uptake.
Angew Chem Int Ed 50(6):1371–1374. doi:10.1002/anie.201005427
111. 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 H 2
production and uptake. Science 326(5958):1384–1387. doi:10.1126/science.1179773
112. Dutta A, Lense S, Hou J, Engelhard MH, Roberts JAS, Shaw WJ (2013) Minimal proton
channel enables H 2 oxidation and production with a water-soluble nickel-based catalyst.
J Am Chem Soc 135(49):18490–18496. doi:10.1021/ja407826d
113. Ginovska-Pangovska B, Dutta A, Reback ML, Linehan JC, Shaw WJ (2014) Beyond the
active site: the impact of the outer coordination sphere on electrocatalysts for hydrogen
production and oxidation. Acc Chem Res 47(8):2621–2630. doi:10.1021/ar5001742
114. Dutta A, Roberts JAS, Shaw WJ (2014) Arginine-containing ligands enhance H2 oxidation
catalyst performance. Angew Chem Int Ed Engl 53(25):6487–6491. doi:10.1002/anie.
201402304
115. Dutta A, DuBois DL, Roberts JAS, Shaw WJ (2014) Amino acid modified Ni catalyst
exhibits reversible H 2 oxidation/production over a broad pH range at elevated temperatures.
Proc Natl Acad Sci U S A 111(46):16286–16291. doi:10.1073/pnas.1416381111
116. Yang Y, Wang M, Xue L, Zhang F, Chen L, Ahlquist MSG, Sun L (2014) Nickel complex
with internal bases as efficient molecular catalyst for photochemical H 2 production.
ChemSusChem 7(10):2889–2897. doi:10.1002/cssc.201402381
268
L. Gan et al.