Redox-Active Ligand Assisted Multielectron Catalysis: A Case of Electrocatalyzed CO2-to-CO Conversion DOI Creative Commons

Wen-Wen Yong,

Hongtao Zhang,

Yu‐Hua Guo

et al.

ACS Organic & Inorganic Au, Journal Year: 2023, Volume and Issue: 3(6), P. 384 - 392

Published: Aug. 22, 2023

The selective reduction of carbon dioxide remains a significant challenge due to the complex multielectron/proton transfer process, which results in high kinetic barrier and production diverse products. Inspired by electrostatic H-bonding interactions observed second sphere [NiFe]-CODH enzyme, researchers have extensively explored these regulate proton transfer, stabilize intermediates, ultimately improve performance catalytic CO2 reduction. In this work, series cobalt(II) tetraphenylporphyrins with varying numbers redox-active nitro groups were synthesized evaluated as electrocatalysts. Analyses redox properties complexes revealed consistent relationship between number corresponding accepted electron ligand at −1.59 V vs. Fc+/0. Among catalysts tested, TNPPCo four exhibited most efficient activity turnover frequency 4.9 × 104 s–1 onset potential 820 mV more positive than that parent TPPCo. Furthermore, frequencies increased higher groups. These demonstrate promising design strategy incorporating multielectron ligands into enhance performance.

Language: Английский

Modulating the Primary and Secondary Coordination Spheres of Single Ni(II) Sites in Metal–Organic Frameworks for Boosting Photocatalysis DOI
Ge Yang, Denan Wang, Yang Wang

et al.

Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: 146(15), P. 10798 - 10805

Published: April 5, 2024

Though the coordination environment of single metal sites has been recognized to be great importance in promoting catalysis, influence simultaneous precise modulation primary and secondary spheres on catalysis remains largely unknown. Herein, a series Ni(II) with altered have installed onto metal–organic frameworks (MOFs) UiO-67 skeleton, affording UiO–Ni–X–Y (X = S, O; Y H, Cl, CF3) X spheres, respectively. Upon deposition CdS nanoparticles, resulting composites present high photocatalytic H2 production rates, which optimized CdS/UiO–Ni–S–CF3 exhibits an excellent activity 13.44 mmol g–1, ∼500 folds pristine catalyst (29.6 μmol g–1 for CdS/UiO), 8 h, highlighting key role microenvironment around Ni sites. Charge kinetic analysis theoretical calculation results demonstrate that charge transfer dynamics reaction energy barrier are closely correlated their spheres. This work manifests advantages MOFs fabrication structurally catalysts elucidation particular influences catalytic performance.

Language: Английский

Citations

27
Hydrogenase and Nitrogenase: Key Catalysts in Biohydrogen Production DOI Creative Commons
Jinsong Xuan,

Lingling He,

Wen Wen

et al.

Molecules, Journal Year: 2023, Volume and Issue: 28(3), P. 1392 - 1392

Published: Feb. 1, 2023

Hydrogen with high energy content is considered to be a promising alternative clean source. Biohydrogen production through microbes provides renewable and immense hydrogen supply by utilizing raw materials such as inexhaustible natural sunlight, water, even organic waste, which supposed solve the two problems of “energy environment protection” at same time. Hydrogenases nitrogenases are classes key enzymes involved in biohydrogen can applied under different biological conditions. Both research on enzymatic catalytic mechanisms innovations techniques important necessary for application production. In this review, we introduce structures related production, summarize recent genetic engineering works enhance describe chemical efforts novel synthetic artificial inspired biocatalysts. Continual studies types future will further improve efficiency contribute economic feasibility an

Language: Английский

Citations

38
Microbial gas fermentation technology for sustainable food protein production DOI

Carlos Woern,

Lutz Großmann

Biotechnology Advances, Journal Year: 2023, Volume and Issue: 69, P. 108240 - 108240

Published: Aug. 28, 2023

Language: Английский

Citations

26
Resource utilization of carbon dioxide and nitrate to produce value-added organonitrogen compounds through an electrochemical approach DOI
Kailun Yu, Hui Wang, Wenchao Yu

et al.

Applied Catalysis B Environment and Energy, Journal Year: 2023, Volume and Issue: 341, P. 123292 - 123292

Published: Sept. 16, 2023

Language: Английский

Citations

26
Comproportionation of CO2 and Cellulose to Formate Using a Floating Semiconductor‐Enzyme Photoreforming Catalyst DOI Creative Commons
Erwin Lam, Melanie Miller, Stuart Linley

et al.

Angewandte Chemie International Edition, Journal Year: 2023, Volume and Issue: 62(20)

Published: March 8, 2023

Abstract Formate production via both CO 2 reduction and cellulose oxidation in a solar‐driven process is achieved by semi‐artificial biohybrid photocatalyst consisting of immobilized formate dehydrogenase on titanium dioxide (TiO | FDH ) producing up to 1.16±0.04 mmol g −1 24 hours at 30 °C 101 kPa under anaerobic conditions. Isotopic labeling experiments with 13 C‐labeled substrates support the mechanism stoichiometric formation through redox half‐reactions. TiO was further hollow glass microspheres perform more practical floating photoreforming allowing vertical solar light illumination optimal exposure real sunlight. Enzymatic depolymerization coupled catalyst generates 0.36±0.04 per m irradiation area after hours. This work demonstrates synergistic valorization solid gaseous waste streams using aqueous solution will thus provide inspiration for development future waste‐to‐chemical conversion strategies.

Language: Английский

Citations

24
Hydrogenase as the basis for green hydrogen production and utilization DOI
Haishuo Ji, Lei Wan, Yanxin Gao

et al.

Journal of Energy Chemistry, Journal Year: 2023, Volume and Issue: 85, P. 348 - 362

Published: July 1, 2023

Language: Английский

Citations

22
Bioinspired Catalyst Design Principles: Progress in Emulating Properties of Enzymes in Synthetic Catalysts DOI
Bojana Ginovska, Oliver Y. Gutiérrez,

Abhi Karkamkar

et al.

ACS Catalysis, Journal Year: 2023, Volume and Issue: 13(18), P. 11883 - 11901

Published: Aug. 25, 2023

Catalysis enables many aspects of modern life, including fuels, products, plastics, and medicines. Recent advances in catalysis have enabled us to realize higher efficiencies new processes. Ideally, we seek achieve high rates selective conversions using catalysts derived from abundantly available elements operating under mild conditions, specifically lower reaction temperatures pressures. Such could enable decentralized, on-demand synthesis chemicals energy carriers. Nature has demonstrated the feasibility this approach with enzymes, which showcase catalytic processes at low pressures nonprecious metals. Current thinking holds that addition active site, complexity enzyme structure, protein scaffold, is also critical achieving performance. Recreating environment been a long-standing scientific goal. However, still understand functions enzymes better than de novo design mimic features, while retaining their activity selectivity more demanding conditions. In Perspective, will critically examine four key areas catalyst incorporate chemical structural properties into synthetic catalysts: (i) use confinement enhance activity, (ii) tailoring around (iii) proton transport, (iv) bifunctionality cooperativity.

Language: Английский

Citations

22
Bioinspired Binickel Catalyst for Carbon Dioxide Reduction: The Importance of Metal–ligand Cooperation DOI Creative Commons
Yao Xiao, Fei Xie,

Hongtao Zhang

et al.

JACS Au, Journal Year: 2024, Volume and Issue: 4(3), P. 1207 - 1218

Published: March 11, 2024

Catalyst design for the efficient CO2 reduction reaction (CO2RR) remains a crucial challenge conversion of to fuels. Natural Ni–Fe carbon monoxide dehydrogenase (NiFe-CODH) achieves reversible and CO at nearly thermodynamic equilibrium potential, which provides template developing CO2RR catalysts. However, compared with natural enzyme, most biomimetic synthetic complexes exhibit negligible catalytic activities, emphasizes significance effective bimetallic cooperation activation. Enlightened by synergy, we herein report dinickel complex, NiIINiII(bphpp)(AcO)2 (where NiNi(bphpp) is derived from H2bphpp = 2,9-bis(5-tert-butyl-2-hydroxy-3-pyridylphenyl)-1,10-phenanthroline) electrocatalytic CO, exhibits remarkable reactivity approximately 5 times higher than that mononuclear Ni catalyst. Electrochemical computational studies have revealed redox-active phenanthroline moiety effectively modulates electron injection transfer akin [Fe3S4] cluster in NiFe-CODH, secondary site facilitates C–O bond activation cleavage through mediation Lewis acid characteristics. Our work underscores significant role catalysis valuable guidance rational

Language: Английский

Citations

13
Outer-sphere effects on the O2 sensitivity, catalytic bias and catalytic reversibility of hydrogenases DOI Creative Commons
Andrea Fasano, Vincent Fourmond, Christophe Léger

et al.

Chemical Science, Journal Year: 2024, Volume and Issue: 15(15), P. 5418 - 5433

Published: Jan. 1, 2024

The comparison of homologous hydrogenases, in which the same inorganic active site is surrounded by a variable protein matrix, has demonstrated that residues are remote from may have great influence on catalytic properties.

Language: Английский

Citations

8
Nitrogenase resurrection and the evolution of a singular enzymatic mechanism DOI Creative Commons
Amanda K. Garcia, Derek F. Harris, Alex Rivier

et al.

eLife, Journal Year: 2023, Volume and Issue: 12

Published: Feb. 17, 2023

The planetary biosphere is powered by a suite of key metabolic innovations that emerged early in the history life. However, it unknown whether life has always followed same set strategies for performing these critical tasks. Today, microbes access atmospheric sources bioessential nitrogen through activities just one family enzymes, nitrogenases. Here, we show only dinitrogen reduction mechanism known to date an ancient feature conserved from nitrogenase ancestors. We designed paleomolecular engineering approach wherein ancestral genes were phylogenetically reconstructed and inserted into genome diazotrophic bacterial model, Azotobacter vinelandii, enabling integrated assessment both vivo functionality purified biochemistry. Nitrogenase ancestors are active robust variable incorporation or more protein subunits. Further, find all exhibit reversible enzymatic reduction, specifically evidenced hydrogen inhibition, which also exhibited extant A. vinelandii isozymes. Our results suggest may have been constrained its sampling sequence space catalyze most energetically challenging biochemical reactions nature. experimental framework established here essential probing how shaped within dynamic, cellular context sustain globally consequential metabolism.

Language: Английский

Citations

21