Electrocatalytic Hydrogen Evolution with Gallium Hydride and Ligand-centered Reduction

Overview

Journal Chem Sci

Publisher Royal Society of Chemistry

Specialty Chemistry

Date 2019 Mar 19

PMID 30881656

Citations 3

Authors

Ni Wang

Haitao Lei

Zongyao Zhang

Jianfeng Li

Wei Zhang

Rui Cao

Affiliations

Soon will be listed here.

Abstract

Ga chloride tetrakis(pentafluorophenyl)porphyrin () was synthesized and shown to be a highly active and stable post-transition metal-based electrocatalyst for the hydrogen evolution reaction (HER). Electrochemical and spectroscopic studies indicate that both the first and second reduction events of are ligand-centered. The 2e-reduced form reacts with a proton to give Ga-H species (-H), which undergoes protonolysis with Brønsted acids to produce H. The identification of key intermediates , , and -H leads to a catalytic cycle, which is valuable for the fundamental understanding of the HER. This study presents a rare but highly active HER electrocatalyst with unusual features, including ligand-centered electron transfer and formation of post-transition metal hydride.

Citing Articles

A comprehensive review on the electrochemical parameters and recent material development of electrochemical water splitting electrocatalysts.

Raveendran A, Chandran M, Dhanusuraman R RSC Adv. 2023; 13(6):3843-3876.

PMID: 36756592 PMC: 9890951. DOI: 10.1039/d2ra07642j.

E-waste recycled materials as efficient catalysts for renewable energy technologies and better environmental sustainability.

Seif R, Salem F, Allam N Environ Dev Sustain. 2023; :1-36.

PMID: 36691418 PMC: 9848041. DOI: 10.1007/s10668-023-02925-7.

Recent developments in the chemistry of non-trigonal pnictogen pincer compounds: from bonding to catalysis.

Abbenseth J, Goicoechea J Chem Sci. 2021; 11(36):9728-9740.

PMID: 34094237 PMC: 8162179. DOI: 10.1039/d0sc03819a.

References

Senge M, Kalisch W, Bischoff I . The reaction of porphyrins with organolithium reagents. Chemistry. 2000; 6(15):2721-38. DOI: 10.1002/1521-3765(20000804)6:15<2721::aid-chem2721>3.0.co;2-z. View

Felton G, Glass R, Lichtenberger D, Evans D . Iron-only hydrogenase mimics. Thermodynamic aspects of the use of electrochemistry to evaluate catalytic efficiency for hydrogen generation. Inorg Chem. 2006; 45(23):9181-4. DOI: 10.1021/ic060984e. View

Robinson G, Tang C, Koppe R, Cowley A, Himmel H . A new class of binuclear gallium hydrides: synthesis and properties of [{GaCl(hpp)H}2] (hpp=1,3,4,6,7,8-hexahydro-2H-pyrimido[1,2-a]pyrimidate). Chemistry. 2007; 13(9):2648-54. DOI: 10.1002/chem.200600807. View

Sheldrick G . A short history of SHELX. Acta Crystallogr A. 2007; 64(Pt 1):112-22. DOI: 10.1107/S0108767307043930. View

DiPasquale A, Mayer J . Hydrogen peroxide: a poor ligand to gallium tetraphenylporphyrin. J Am Chem Soc. 2008; 130(6):1812-3. DOI: 10.1021/ja077598w. View

Rakowski DuBois M, DuBois D . The roles of the first and second coordination spheres in the design of molecular catalysts for H2 production and oxidation. Chem Soc Rev. 2008; 38(1):62-72. DOI: 10.1039/b801197b. View

Seifert A, Scheid D, Linti G, Zessin T . Oxidative addition reactions of element-hydrogen bonds with different polarities to a gallium(I) compound. Chemistry. 2009; 15(44):12114-20. DOI: 10.1002/chem.200901403. View

Dempsey J, Brunschwig B, Winkler J, Gray H . Hydrogen evolution catalyzed by cobaloximes. Acc Chem Res. 2009; 42(12):1995-2004. DOI: 10.1021/ar900253e. View

Karunadasa H, Chang C, Long J . A molecular molybdenum-oxo catalyst for generating hydrogen from water. Nature. 2010; 464(7293):1329-33. DOI: 10.1038/nature08969. View

10.

Kaur-Ghumaan S, Schwartz L, Lomoth R, Stein M, Ott S . Catalytic hydrogen evolution from mononuclear iron(II) carbonyl complexes as minimal functional models of the [FeFe] hydrogenase active site. Angew Chem Int Ed Engl. 2010; 49(43):8033-6. DOI: 10.1002/anie.201002719. View

11.

Fourmond V, Jacques P, Fontecave M, Artero V . H2 evolution and molecular electrocatalysts: determination of overpotentials and effect of homoconjugation. Inorg Chem. 2010; 49(22):10338-47. DOI: 10.1021/ic101187v. View

12.

Lee C, Dogutan D, Nocera D . Hydrogen generation by hangman metalloporphyrins. J Am Chem Soc. 2011; 133(23):8775-7. DOI: 10.1021/ja202136y. View

13.

Helm M, Stewart M, Bullock R, Rakowski DuBois M, DuBois D . A synthetic nickel electrocatalyst with a turnover frequency above 100,000 s⁻¹ for H₂ production. Science. 2011; 333(6044):863-6. DOI: 10.1126/science.1205864. View

14.

Stubbert B, Peters J, Gray H . Rapid water reduction to H2 catalyzed by a cobalt bis(iminopyridine) complex. J Am Chem Soc. 2011; 133(45):18070-3. DOI: 10.1021/ja2078015. View

15.

McCrory C, Uyeda C, Peters J . Electrocatalytic hydrogen evolution in acidic water with molecular cobalt tetraazamacrocycles. J Am Chem Soc. 2012; 134(6):3164-70. DOI: 10.1021/ja210661k. View

16.

Singh W, Baine T, Kudo S, Tian S, Ma X, Zhou H . Electrocatalytic and photocatalytic hydrogen production in aqueous solution by a molecular cobalt complex. Angew Chem Int Ed Engl. 2012; 51(24):5941-4. DOI: 10.1002/anie.201200082. View

17.

Rose M, Gray H, Winkler J . Hydrogen generation catalyzed by fluorinated diglyoxime-iron complexes at low overpotentials. J Am Chem Soc. 2012; 134(20):8310-3. DOI: 10.1021/ja300534r. View

18.

Thoi V, Sun Y, Long J, Chang C . Complexes of earth-abundant metals for catalytic electrochemical hydrogen generation under aqueous conditions. Chem Soc Rev. 2012; 42(6):2388-400. DOI: 10.1039/c2cs35272a. View

19.

Carroll M, Barton B, Rauchfuss T, Carroll P . Synthetic models for the active site of the [FeFe]-hydrogenase: catalytic proton reduction and the structure of the doubly protonated intermediate. J Am Chem Soc. 2012; 134(45):18843-52. PMC: 3514462. DOI: 10.1021/ja309216v. View

20.

Liu T, DuBois D, Bullock R . An iron complex with pendent amines as a molecular electrocatalyst for oxidation of hydrogen. Nat Chem. 2013; 5(3):228-233. DOI: 10.1038/nchem.1571. View