Catalyst Self-assembly Accelerates Bimetallic Light-driven Electrocatalytic H Evolution in Water

Overview

Journal Nat Chem

Specialty Chemistry

Date 2024 Mar 26

PMID 38528106

Authors

Isaac N Cloward

Tianfei Liu

Jamie Rose

Tamara Jurado

Annabell G Bonn

Matthew B Chambers

Catherine L Pitman

Marc A Ter Horst

Alexander J M Miller

Affiliations

Soon will be listed here.

Abstract

Hydrogen evolution is an important fuel-generating reaction that has been subject to mechanistic debate about the roles of monometallic and bimetallic pathways. The molecular iridium catalysts in this study undergo photoelectrochemical dihydrogen (H) evolution via a bimolecular mechanism, providing an opportunity to understand the factors that promote bimetallic H-H coupling. Covalently tethered diiridium catalysts evolve H from neutral water faster than monometallic catalysts, even at lower overpotential. The unexpected origin of this improvement is non-covalent supramolecular self-assembly into nanoscale aggregates that efficiently harvest light and form H-H bonds. Monometallic catalysts containing long-chain alkane substituents leverage the self-assembly to evolve H from neutral water at low overpotential and with rates close to the expected maximum for this light-driven water splitting reaction. Design parameters for holding multiple catalytic sites in close proximity and tuning catalyst microenvironments emerge from this work.

Citing Articles

Supramolecular interaction of a molecular catalyst with a polymeric carbon nitride photoanode enhances photoelectrochemical activity and stability at neutral pH.

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PMID: 39323522 PMC: 11418009. DOI: 10.1039/d4sc04678a.

Assembling the pieces to improve catalysis.

Sonea A, Warren J Nat Chem. 2024; 16(5):678-679.

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References

Lewis N, Nocera D . Powering the planet: chemical challenges in solar energy utilization. Proc Natl Acad Sci U S A. 2006; 103(43):15729-35. PMC: 1635072. DOI: 10.1073/pnas.0603395103. View

Walter M, Warren E, McKone J, Boettcher S, Mi Q, Santori E . Solar water splitting cells. Chem Rev. 2010; 110(11):6446-73. DOI: 10.1021/cr1002326. View

Cook T, Dogutan D, Reece S, Surendranath Y, Teets T, Nocera D . Solar energy supply and storage for the legacy and nonlegacy worlds. Chem Rev. 2010; 110(11):6474-502. DOI: 10.1021/cr100246c. View

Esswein A, Nocera D . Hydrogen production by molecular photocatalysis. Chem Rev. 2007; 107(10):4022-47. DOI: 10.1021/cr050193e. View

Berardi S, Drouet S, Francas L, Gimbert-Surinach C, Guttentag M, Richmond C . Molecular artificial photosynthesis. Chem Soc Rev. 2014; 43(22):7501-19. DOI: 10.1039/c3cs60405e. View

Karkas M, Verho O, Johnston E, Akermark B . Artificial photosynthesis: molecular systems for catalytic water oxidation. Chem Rev. 2014; 114(24):11863-2001. DOI: 10.1021/cr400572f. View

Ashford D, Gish M, Vannucci A, Brennaman M, Templeton J, Papanikolas J . Molecular Chromophore-Catalyst Assemblies for Solar Fuel Applications. Chem Rev. 2015; 115(23):13006-49. DOI: 10.1021/acs.chemrev.5b00229. View

Reyes Cruz E, Nishiori D, Wadsworth B, Nguyen N, Hensleigh L, Khusnutdinova D . Molecular-Modified Photocathodes for Applications in Artificial Photosynthesis and Solar-to-Fuel Technologies. Chem Rev. 2022; 122(21):16051-16109. DOI: 10.1021/acs.chemrev.2c00200. View

Costentin C, Dridi H, Saveant J . Molecular catalysis of H2 evolution: diagnosing heterolytic versus homolytic pathways. J Am Chem Soc. 2014; 136(39):13727-34. DOI: 10.1021/ja505845t. View

10.

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

11.

Valdez C, Dempsey J, Brunschwig B, Winkler J, Gray H . Catalytic hydrogen evolution from a covalently linked dicobaloxime. Proc Natl Acad Sci U S A. 2012; 109(39):15589-93. PMC: 3465440. DOI: 10.1073/pnas.1118329109. View

12.

Rivier L, Peljo P, Maye S, Mendez M, Vrubel H, Vannay L . Mechanistic Study on the Photogeneration of Hydrogen by Decamethylruthenocene. Chemistry. 2019; 25(55):12769-12779. DOI: 10.1002/chem.201902353. View

13.

Huang J, Sun J, Wu Y, Turro C . Dirhodium(II,II)/NiO Photocathode for Photoelectrocatalytic Hydrogen Evolution with Red Light. J Am Chem Soc. 2021; 143(3):1610-1617. DOI: 10.1021/jacs.0c12171. View

14.

Chambers M, Kurtz D, Pitman C, Brennaman M, Miller A . Efficient Photochemical Dihydrogen Generation Initiated by a Bimetallic Self-Quenching Mechanism. J Am Chem Soc. 2016; 138(41):13509-13512. DOI: 10.1021/jacs.6b08701. View

15.

Pitman C, Brereton K, Miller A . Aqueous Hydricity of Late Metal Catalysts as a Continuum Tuned by Ligands and the Medium. J Am Chem Soc. 2016; 138(7):2252-60. PMC: 4768292. DOI: 10.1021/jacs.5b12363. View

16.

Rountree E, McCarthy B, Eisenhart T, Dempsey J . Evaluation of homogeneous electrocatalysts by cyclic voltammetry. Inorg Chem. 2014; 53(19):9983-10002. DOI: 10.1021/ic500658x. View

17.

Wadsworth B, Beiler A, Khusnutdinova D, Reyes Cruz E, Moore G . Interplay between Light Flux, Quantum Efficiency, and Turnover Frequency in Molecular-Modified Photoelectrosynthetic Assemblies. J Am Chem Soc. 2019; 141(40):15932-15941. DOI: 10.1021/jacs.9b07295. View

18.

Nguyen N, Wadsworth B, Nishiori D, Reyes Cruz E, Moore G . Understanding and Controlling the Performance-Limiting Steps of Catalyst-Modified Semiconductors. J Phys Chem Lett. 2020; 12(1):199-203. DOI: 10.1021/acs.jpclett.0c02386. View

19.

Costentin C, Passard G, Saveant J . Benchmarking of homogeneous electrocatalysts: overpotential, turnover frequency, limiting turnover number. J Am Chem Soc. 2015; 137(16):5461-7. DOI: 10.1021/jacs.5b00914. View

20.

Weberg A, Murphy R, Tomson N . Oriented internal electrostatic fields: an emerging design element in coordination chemistry and catalysis. Chem Sci. 2022; 13(19):5432-5446. PMC: 9116365. DOI: 10.1039/d2sc01715f. View