Unveiling the Proton‐Feeding Effect in Sulfur‐Doped Fe−N−C Single‐Atom Catalyst for Enhanced CO₂ Electroreduction

Angewandte Chemie International Edition, Год журнала: 2022, Номер 61(32)

Опубликована: Июнь 8, 2022

Heteroatom-doping in metal-nitrogen-carbon single-atom catalysts (SACs) is considered a powerful strategy to promote the electrocatalytic CO2 reduction reaction (CO2 RR), but origin of enhanced catalytic activity still elusive. Here, we disclose that sulfur doping induces an obvious proton-feeding effect for RR. The model SAC catalyst with second-shell FeN4 (Fe1 -NSC) was verified by X-ray absorption spectroscopy and aberration-corrected scanning transmission electron microscopy. Fe1 -NSC exhibits superior RR performance compared sulfur-free most reported Fe-based SACs, maximum CO Faradaic efficiency 98.6 % turnover frequency 1197 h-1 . Kinetic analysis situ characterizations confirm accelerates H2 O activation feeds sufficient protons promoting conversion *COOH, which also corroborated theoretical results. This work deepens understanding mechanism based on catalysts.

Язык: Английский

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MOF Encapsulating N‐Heterocyclic Carbene‐Ligated Copper Single‐Atom Site Catalyst towards Efficient Methane Electrosynthesis

Angewandte Chemie International Edition, Год журнала: 2021, Номер 61(4)

Опубликована: Ноя. 12, 2021

The exploitation of highly efficient carbon dioxide reduction (CO2 RR) electrocatalyst for methane (CH4 ) electrosynthesis has attracted great attention the intermittent renewable electricity storage but remains challenging. Here, N-heterocyclic carbene (NHC)-ligated copper single atom site (Cu SAS) embedded in metal-organic framework is reported (2Bn-Cu@UiO-67), which can achieve an outstanding Faradaic efficiency (FE) 81 % CO2 to CH4 at -1.5 V vs. RHE with a current density 420 mA cm-2 . FE our catalyst above 70 within wide potential range and achieves unprecedented turnover frequency (TOF) 16.3 s-1 σ donation NHC enriches surface electron Cu SAS promotes preferential adsorption CHO* intermediates. porosity facilitates diffusion 2Bn-Cu, significantly increasing availability each catalytic center.

Язык: Английский

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Highly Selective Tandem Electroreduction of CO₂ to Ethylene over Atomically Isolated Nickel–Nitrogen Site/Copper Nanoparticle Catalysts

Angewandte Chemie International Edition, Год журнала: 2021, Номер 60(48), С. 25485 - 25492

Опубликована: Сен. 17, 2021

Herein, an effective tandem catalysis strategy is developed to improve the selectivity of CO2 RR towards C2 H4 by multiple distinct catalytic sites in local vicinity. An earth-abundant elements-based electrocatalyst PTF(Ni)/Cu constructed uniformly dispersing Cu nanoparticles (NPs) on porphyrinic triazine framework anchored with atomically isolated nickel-nitrogen (PTF(Ni)) for enhanced produce . The Faradaic efficiency reaches 57.3 % at -1.1 V versus reversible hydrogen electrode (RHE), which about 6 times higher than non-tandem catalyst PTF/Cu, produces CH4 as major carbon product. operando infrared spectroscopy and theoretic density functional theory (DFT) calculations reveal that high concentration CO generated PTF(Ni) can facilitate C-C coupling form nearby NP sites. work offers avenue design electrocatalysts highly selective multicarbon products via a route.

Язык: Английский

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Thermo-, Electro-, and Photocatalytic CO₂ Conversion to Value-Added Products over Porous Metal/Covalent Organic Frameworks

Accounts of Chemical Research, Год журнала: 2022, Номер 55(20), С. 2978 - 2997

Опубликована: Сен. 26, 2022

ConspectusThe continuing increase of the concentration atmospheric CO2 has caused many environmental issues including climate change. Catalytic conversion using thermochemical, electrochemical, and photochemical methods is a potential technique to decrease simultaneously obtain value-added chemicals. Due high energy barrier however, this method still far from large-scale applications which requires activity, selectivity, stability. Therefore, development efficient catalysts convert different products urgent. With their well-engineered pores chemical compositions, surface area, elevated adsorption capability, adjustable active sites, porous crystalline frameworks metal-organic (MOFs) covalent organic (COFs) are materials for catalytic conversion. Here, we summarize our recent work on MOFs COFs thermocatalytic, electrocatalytic, photocatalytic describe structure-activity relationships that could guide design effective catalysts.The first section paper describes imidazolium-functionalized MOFs, liquid cationic with nucleophilic halogen ions, can promote thermocatalytically cycloaddition reaction epoxides toward cyclic carbonates at one bar pressure. A MOF takes role reservoir tackle low local concentrations in gas-liquid-solid heterogeneous reactions. Imidazolium-functionalized ions avoid use cocatalysts, leads milder more facile experimental conditions separation processes.In dealing electrocatalytic reduction (CO2RR), developed series conductive framework fast electron transmission capabilities, afford current densities outperform traditional COF have been reported. The intrinsically two-dimensional 2D nanosheets based fully π-conjugated phthalocyanine motif excellent transport capability were prepared, strong transporters also integrated into metalloporphyrin-based CO2RR. Cu2O quantum dots Cu nanoparticles (NPs) be uniformly dispersed MOFs/COFs synergistic and/or tandem electrocatalysts, achieve highly selective production CH4 or C2H4 CO2RR.A third efforts facilitate electron-hole photocatalysis. Our focus regulation coordination spheres fabrication architecture heterojunctions, engineering films reduction.Finally, discuss several problems associated studies consider some prospects

Язык: Английский

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Two-Dimensional Conjugated Metal–Organic Frameworks for Electrocatalysis: Opportunities and Challenges

ACS Nano, Год журнала: 2022, Номер 16(2), С. 1759 - 1780

Опубликована: Янв. 20, 2022

A highly effective electrocatalyst is the central component of advanced electrochemical energy conversion. Recently, two-dimensional conjugated metal-organic frameworks (2D c-MOFs) have emerged as a class promising electrocatalysts because their advantages including 2D layered structure with high in-plane conjugation, intrinsic electrical conductivity, permanent pores, large surface area, chemical stability, and structural diversity. In this Review, we summarize recent advances c-MOF for First, introduce design principles synthetic strategies reported c-MOFs, well functional electrocatalysis. Subsequently, present representative in various reactions, such hydrogen/oxygen evolution, reduction reactions oxygen, carbon dioxide, nitrogen. We highlight property tuning to boost catalytic performance, offer our perspectives regard challenges be overcome.

Язык: Английский

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Challenges and Opportunities in Electrocatalytic CO₂ Reduction to Chemicals and Fuels

Angewandte Chemie International Edition, Год журнала: 2022, Номер 61(49)

Опубликована: Авг. 22, 2022

The global temperature increase must be limited to below 1.5 °C alleviate the worst effects of climate change. Electrocatalytic CO

Язык: Английский

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Electrochemical CO₂reduction to C₂₊products using Cu-based electrocatalysts: A review

Deleted Journal, Год журнала: 2022, Номер 1, С. e9120021 - e9120021

Опубликована: Июль 4, 2022

With the disruptive carbon cycle being blamed for global warming, plausible electrocatalytic CO₂ reduction reaction (CO₂RR) to form valuable C₂₊ hydrocarbons and feedstock is becoming a hot topic. Cu-based electrocatalysts have been proven be excellent CO₂RR alternatives high energy value-added products in this regard. However, selectivity of via catalysts suffers from overpotential, slow kinetics, low selectivity. This review attempts discuss various cutting-edge strategies understanding catalytic design such as catalyst surface engineering, tuning Cu bandgap alloying, nanocatalysis, effect electrolyte pH on morphology. The most recent advances in situ spectroscopy computational techniques are summarized fully comprehend mechanisms, structural transformation/degradation crystal facet loss with subsequent effects activity. Furthermore, approaches interactions discussed four key perspectives: single-atom catalysts, interfacial metal-organic frameworks, polymer-incorporated materials, which provide new insights into products. Finally, major challenges outlined, potential prospects rational robust proposed. integration mechanistic step forward promising advancement technology industrial applications.

Язык: Английский

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Localized Alkaline Environment via In Situ Electrostatic Confinement for Enhanced CO₂-to-Ethylene Conversion in Neutral Medium

Journal of the American Chemical Society, Год журнала: 2023, Номер 145(11), С. 6339 - 6348

Опубликована: Март 9, 2023

Electrocatalytic CO2 reduction reaction (CO2RR) is one of the most promising routes to facilitate carbon neutrality. An alkaline electrolyte typically needed promote production valuable multi-carbon molecules (such as ethylene). However, between and OH- consumes a significant quantity CO2/alkali causes rapid decay CO2RR selectivity stability. Here, we design catalyst-electrolyte interface with an effective electrostatic confinement in situ generated improve ethylene electrosynthesis from neutral medium. In Raman measurements indicate direct correlation intensities surface Cu-CO Cu-OH species, suggesting promoted C-C coupling enrichment OH-. Thus, report CO2-to-ethylene Faradaic efficiency (FE) 70% partial current density 350 mA cm-2 at -0.89 V vs reversible hydrogen electrode. Furthermore, system demonstrated 50 h stable operation 300 average FE ∼68%. This study offers universal strategy tune micro-environment, significantly improved 64.5% was obtained even acidic electrolytes (pH = 2).

Язык: Английский

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Ternary heterojunction in rGO-coated Ag/Cu2O catalysts for boosting selective photocatalytic CO2 reduction into CH4

Applied Catalysis B Environment and Energy, Год журнала: 2022, Номер 311, С. 121371 - 121371

Опубликована: Апрель 6, 2022

Язык: Английский

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A rational design of functional porous frameworks for electrocatalytic CO₂reduction reaction

Chemical Society Reviews, Год журнала: 2023, Номер 52(4), С. 1382 - 1427

Опубликована: Янв. 1, 2023

Rational design of functional porous frameworks for electrocatalytic CO 2 reduction reaction.

Язык: Английский

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