Dual-atom catalysts with microenvironment regulation for water electrolysis

Journal of Materials Chemistry A, Journal Year: 2024, Volume and Issue: 12(39), P. 26316 - 26349

Published: Jan. 1, 2024

Dual-atom catalysts (DACs) have emerged as highly promising and efficient for water electrolysis, primarily due to their distinct dual-atom site effects.

Language: Английский

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Biomimetic Approaches for Renewable Energy and Carbon Neutrality: Advancing Nature‐Inspired Approaches for Sustainable Development

Sustainable Development, Journal Year: 2025, Volume and Issue: unknown

Published: April 21, 2025

ABSTRACT As global non‐renewable energy sources depletes, achieving carbon neutrality by 2050 has become an urgent international priority, as outlined in the Paris Agreement. Renewable transition demands environmentally sustainable, economically viable, and energy‐efficient innovations. Thus, biomimetic architecture, devices, structures, materials, drawing design inspiration from natural systems, emerge promising players addressing climate issues within urban environments. This review critically analyzes 126 publications on research sustainable (2010–2024), selected 188 screened across major databases using targeted keywords. By integrating human ingenuity with approaches offer strategies for efficiency resilience. However, significant challenges remain, including high investment prices, industrial change, insufficient collaboration, hence coordinated efforts are needed to implement integrated policies, foster innovation, enhance cooperation order achieve neutrality. Biomimetic show potential building a more climate‐resilient future.

Language: Английский

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Unveiling the Activity and Mechanism Alterations by Pyrene Decoration on a Co(II) Macrocyclic Catalyst for CO₂ Reduction

ChemSusChem, Journal Year: 2024, Volume and Issue: 17(11)

Published: Jan. 30, 2024

Abstract Mechanistic studies involving characterization of crucial intermediates are desirable for rational optimization molecular catalysts toward CO 2 reduction, while fundamental challenges associated with such studies. Herein we present the systematic mechanistic investigations on a pyrene‐appended Co II macrocyclic catalyst in comparison its pyrene‐free prototype. The comparative results also verify reasons higher catalytic activity pyrene‐tethered noble‐metal‐free photoreduction various photosensitizers, where remarkable apparent quantum yield 36±3 % at 425 nm can be obtained selective production. Electrochemical and spectroelectrochemical conjunction DFT calculations between two have characterized key CO‐bound revealed their different CO‐binding behavior, demonstrating that pyrene group endows corresponding lower potential, stability, greater ease release, all which contribute to better performance.

Language: Английский

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A Bio‐Inspired Bimetallic Fe−M Catalyst for Electro‐ and Photochemical CO₂ Reduction

ChemCatChem, Journal Year: 2024, Volume and Issue: 16(10)

Published: Feb. 5, 2024

Abstract The conversion of CO 2 into fuels or commodity chemicals by electrochemical photochemical reduction is a promising strategy to relieve the ongoing energy crisis and increasing environmental pollution. Inspired naturally occurring bimetalloenzymes, we have designed hetero–bimetallic catalysts ( FeM ) that involve linking an iron tetraphenylporphyrin FeP with tripyridylamine (TPA) moiety, which provides distal chelating site for Cu 2+ Zn . We found introduction greatly enhances its efficiency as catalyst To gain insights observed synergistic effect, performed mechanistic studies together density functional theory (DFT) calculations. Our results show activates towards due Lewis acidity; it also functions oxo acceptor from efficient visible‐light‐driven using either [Ru(bpy) 3 ] Cl fac ‐Ir(ppy) (where bpy=2,2’‐bipyridine, ppy=2‐phenylpyridine) photosensitizer 1,3‐dimethyl‐2‐phenyl‐2,3‐dihydro‐1H‐benzo[d] imidazole (BIH) sacrificial reductant. Again, catalytic enhanced presence provide general design series hetero‐bimetallic

Language: Английский

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Computational Modeling of Electrocatalysts for CO₂ Reduction: Probing the Role of Primary, Secondary, and Outer Coordination Spheres

Accounts of Chemical Research, Journal Year: 2025, Volume and Issue: unknown

Published: Jan. 27, 2025

ConspectusIn the search for efficient and selective electrocatalysts capable of converting greenhouse gases to value-added products, enzymes found in naturally existing bacteria provide basis most approaches toward electrocatalyst design. Ni,Fe-carbon monoxide dehydrogenase (Ni,Fe-CODH) is one such enzyme, with a nickel-iron-sulfur cluster named C-cluster, where CO2 binds converted CO at high rates near thermodynamic potential. In this Account, we divide enzyme's catalytic contributions into three categories based on location function. We also discuss how computational techniques crucial insight implementing these findings homogeneous reduction electrocatalysis design principles. The binding sites (e.g., Ni "unique" Fe ion) along ligands that support it iron-sulfur cluster) form primary coordination sphere. This replicated molecular via metal center ligand framework substrate binds. sphere has direct impact electronic configuration catalyst. By computationally modeling series Co complexes bipyridyl-N-heterocyclic carbene frameworks varying degrees planarity, were able closely examine controls product distribution between H2 catalysts. secondary (SCS) Ni,Fe-CODH contains residues proximal active site pocket hydrogen-bonding stabilizations necessary reaction proceed. Enhancing SCS when synthesizing new catalysts involves substituting functional groups onto interaction substrate. To analyze endless possible substitutions, are ideal deciphering intricacies substituent effects, as demonstrated an array imidazolium-functionalized Mn Re bipyridyl tricarbonyl complexes. examining electrostatic interactions ligand, substrate, proton source lowered activation energy barriers, determined best pinpoint additions. outer comprises remaining parts Ni,Fe-CODH, elaborate protein matrix, solvent interactions, remote metalloclusters. challenge elucidating replicating role vast matrix understandably led localized focus spheres. However, certain portions Ni,Fe-CODH's expansive scaffold suggested be catalytically relevant despite considerable distance from site. Closer studies relatively overlooked areas nature's exceptionally proficient may continually improve upon protocols. Mechanistic analysis cobalt phthalocyanines (CoPc) immobilized carbon nanotubes (CoPc/CNT) reveals microenvironment effects unlock CoPc molecule's previously inaccessible intrinsic ability convert MeOH. Our research suggests incorporating spheres holistic approach vital advancing viability mitigating climate disruption. Computational methods allow us transition states determine minimize key barriers.

Language: Английский

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Electrostatic versus Hydrogen Bonding Control of Selectivity in CO₂ Reduction by Iron Porphyrins

ACS Catalysis, Journal Year: 2025, Volume and Issue: unknown, P. 3595 - 3610

Published: Feb. 13, 2025

Language: Английский

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Origins of HCOOH Selectivity Over CO Mediated by an Unusual Fe(I)-Porphyrin Bearing a β-Substituted Cation

Inorganic Chemistry, Journal Year: 2025, Volume and Issue: unknown

Published: March 5, 2025

Molecular metalloporphyrins have been commonly reported to efficiently catalyze electrochemical CO2-to-CO conversion. Unconventionally, Dey and coworkers that an iron-porphyrin analogue bearing a pendant amine binds with CO2 at the Fe(I) state reduces into formic acid using water molecules as proton sources. However, origins of HCOOH selectivity over conventional CO product, well fundamental mechanistic details, are lacking. In work, theoretical computations were employed fundamentally investigate reaction mechanisms. Our calculations reconfirmed formal Fe(I)-porphyrin would proceed direct CO2-binding step, this behavior could be ascribed significant hydrogen bonding through-space electrostatic interactions between cationic N-H [CO22-]-coordinated species. A two-electron transfer process in key step is found, which estimated consecutively protonation 1e-reduction give rise Fe(III)-COOH Fe(II)-COOH intermediate, respectively. The plays vital roles stabilization C-protonation species yield HCOOH. Moreover, terminal hinder dissociation CO. computational results consistent experimental observations. elucidated, insightful understanding cooperative second-sphere effects provided.

Language: Английский

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Electrocatalytic CO2 Reduction Coupled with Water Oxidation by bi- and Tetranuclear Copper Complexes Based on di-2-pyridyl Ketone Ligand

Molecules, Journal Year: 2025, Volume and Issue: 30(7), P. 1544 - 1544

Published: March 31, 2025

In the field of sustainable energy conversion and storage technologies, copper-based complexes have become a research hotspot due to their efficient stable catalytic performance. The development bifunctional catalysts that can simplify steps, enhance efficiency, reduce catalyst usage has an important area. this study, we successfully synthesized two copper with different geometries utilizing di(2-pyridyl) ketone as ligand, [CuII2L2Cl2]·0.5H2O (1) [Cu4IIL4(OCH3)2](NO3)2 (2) (L = deprotonated methoxy-di-pyridin-2-yl-methanol), which serve homogeneous electrocatalysts for water oxidation CO2 reduction simultaneously. turnover frequency (TOF) 1 2 electrocatalytic are 7.23 s−1 0.31 under almost neutral condition (pH 8.22), respectively. Meanwhile, TOF CO 4.27 8.9 s−1, addition, both remain essentially unchanged during processes, demonstrating good stability. Structural analysis reveals distinct efficiencies originate from geometric configurations: binuclear structure complex facilitates proton-coupled electron transfer oxidation, whereas tetranuclear architecture enhances activation. Complexes represent first molecular capable catalyzing reduction. findings in work open up new avenues advancement artificial photosynthesis simulation

Language: Английский

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Across the Board: Rui Cao on Electrocatalytic CO₂ Reduction

ChemSusChem, Journal Year: 2022, Volume and Issue: 15(21)

Published: Sept. 22, 2022

In this series of articles, the Board Members ChemSusChem review recent research articles that they consider exceptional quality and importance for sustainability. This entry features Prof. Rui Cao, who discusses how tuning second-sphere environments Fe porphyrins can improve activity selectivity CO2 reduction. Substituents with proton relay capability, hydrogen-bonding, electrostatic have significant impact on efficiency electrocatalytic reduction reaction.

Language: Английский

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Two Novel Schiff Base Manganese Complexes as Bifunctional Electrocatalysts for CO2 Reduction and Water Oxidation

Molecules, Journal Year: 2023, Volume and Issue: 28(3), P. 1074 - 1074

Published: Jan. 20, 2023

One mononuclear Mn(III) complex [MnIIIL(H2O)(MeCN)](ClO4) (1) and one hetero-binuclear [(CuIILMnII(H2O)3)(CuIIL)2](ClO4)2·CH3OH (2) have been synthesized with the Schiff base ligand (H2L = N,N′-bis(3-methoxysalicylidene)-1,2-phenylenediamine). Single crystal X-ray structural analysis manifests that ion in 1 has an octahedral coordination structure, whereas Mn(II) 2 possesses a trigonal bipyramidal configuration Cu(II) is four-coordinated square-planar geometry. Electrochimerical catalytic investigation demonstrates two complexes can electrochemically catalyze water oxidation CO2 reduction simultaneously. The environments of Mn(III), Mn(II), ions were provided by (L) labile solvent molecules. coordinately unsaturated environment center perfectly facilitate performance 2. Complexes display over potentials for are 728 mV 216 mV, faradaic efficiencies (FEs) 88% 92%, respectively, as well turnover frequency (TOF) values to CO 0.38 s−1 at −1.65 V 15.97 −1.60 V, respectively. Complex shows much better both than 1, which could be owing reason attributed synergistic action neighboring active sites first compounds coordinated reduction. finding this work offer significant inspiration future development electrocatalysis area.

Language: Английский

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