Metal-organic-framework-based materials as platforms for energy applications

Chem, Год журнала: 2023, Номер 10(1), С. 86 - 133

Опубликована: Окт. 10, 2023

Язык: Английский

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Oxophilicity-Controlled CO₂ Electroreduction to C₂₊ Alcohols over Lewis Acid Metal-Doped Cu^δ+ Catalysts

Journal of the American Chemical Society, Год журнала: 2023, Номер 145(40), С. 21945 - 21954

Опубликована: Сен. 26, 2023

Cu-based electrocatalysts have great potential for facilitating CO2 reduction to produce energy-intensive fuels and chemicals. However, it remains challenging obtain high product selectivity due the inevitable strong competition among various pathways. Here, we propose a strategy regulate adsorption of oxygen-associated active species on Cu by introducing an oxophilic metal, which can effectively improve C2+ alcohols. Theoretical calculations manifested that doping Lewis acid metal Al into affect C–O bond Cu–C breaking toward selectively determining intermediate (shared ethanol ethylene), thus prioritizing pathway. Experimentally, Al-doped catalyst exhibited outstanding Faradaic efficiency (FE) 84.5% with remarkable stability. In particular, alcohol FE could reach 55.2% partial current density 354.2 mA cm–2 formation rate 1066.8 μmol h–1. A detailed experimental study revealed improved strength oxygen surface stabilized key *OC2H5, leading ethanol. Further investigation showed this also be extended other metals.

Язык: Английский

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Membrane Electrode Assembly for Electrocatalytic CO₂ Reduction: Principle and Application

Angewandte Chemie International Edition, Год журнала: 2023, Номер 62(28)

Опубликована: Март 27, 2023

Abstract Electrocatalytic CO 2 reduction reaction (CO RR) in membrane electrode assembly (MEA) systems is a promising technology. Gaseous can be directly transported to the cathode catalyst layer, leading enhanced rate. Meanwhile, there no liquid electrolyte between and anode, which help improve energy efficiency of whole system. The remarkable progress achieved recently points out way realize industrially relevant performance. In this review, we focus on principles MEA for RR, focusing gas diffusion electrodes ion exchange membranes. Furthermore, anode processes beyond oxidation water are considered. Besides, voltage distribution scrutinized identify specific losses related individual components. We also summarize generation different reduced products together with corresponding catalysts. Finally, challenges opportunities highlighted future research.

Язык: Английский

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Efficient acidic hydrogen evolution in proton exchange membrane electrolyzers over a sulfur-doped marcasite-type electrocatalyst

Science Advances, Год журнала: 2023, Номер 9(27)

Опубликована: Июль 5, 2023

Large-scale deployment of proton exchange membrane (PEM) water electrolyzers has to overcome a cost barrier resulting from the exclusive adoption platinum group metal (PGM) catalysts. Ideally, carbon-supported used at cathode should be replaced with PGM-free catalysts, but they often undergo insufficient activity and stability subjecting corrosive acidic conditions. Inspired by marcasite existed under environments in nature, we report sulfur doping-driven structural transformation pyrite-type cobalt diselenide pure counterpart. The resultant catalyst drives hydrogen evolution reaction low overpotential 67 millivolts 10 milliamperes per square centimeter exhibits no degradation after 1000 hours testing acid. Moreover, PEM electrolyzer this as runs stably over 410 1 ampere 60°C. marked properties arise doping that not only triggers formation acid-resistant structure also tailors electronic states (e.g., work function) for improved diffusion electrocatalysis.

Язык: Английский

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Selective CO₂ Reduction to Ethylene Mediated by Adaptive Small‐molecule Engineering of Copper‐based Electrocatalysts

Angewandte Chemie International Edition, Год журнала: 2023, Номер 62(50)

Опубликована: Окт. 30, 2023

Electrochemical CO2 reduction reaction (CO2 RR) over Cu catalysts exhibits enormous potential for efficiently converting to ethylene (C2 H4 ). However, achieving high C2 selectivity remains a considerable challenge due the propensity of undergo structural reconstruction during RR. Herein, we report an in situ molecule modification strategy that involves tannic acid (TA) molecules adaptive regulating Cu-based material pathway facilitates products. An excellent Faraday efficiency (FE) 63.6 % on with current density 497.2 mA cm-2 flow cell was achieved, about 6.5 times higher than pristine catalyst which mainly produce CH4 . The X-ray absorption spectroscopy and Raman studies reveal hydroxyl group TA stabilizes Cuδ+ Furthermore, theoretical calculations demonstrate /Cu0 interfaces lower activation energy barrier *CO dimerization, species stabilize *COH intermediate via hydrogen bonding, thereby promoting production. Such engineering modulated electronic structure provides promising achieve highly selective value-added chemicals.

Язык: Английский

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Quasi‐Topological Intercalation Mechanism of Bi_0.67NbS₂ Enabling 100 C Fast‐Charging for Sodium‐Ion Batteries

Advanced Energy Materials, Год журнала: 2023, Номер 13(25)

Опубликована: Май 17, 2023

Abstract Alloying‐type bismuth with high volumetric capacity has emerged as a promising anode for sodium‐ion batteries but suffers from large volume expansion and continuous pulverization. Herein, coordination constraint strategy is proposed, that is, chemically confining atomic Bi in an intercalation host framework via reconstruction‐favorable linear bonds, enabling novel quasi‐topological mechanism. Specifically, micron‐sized 0.67 NbS 2 synthesized, which the atom linearly coordinated two S atoms interlayer of . The robust Nb−S provides fast ion/electron diffusion channels buffers Na + insertion, endowing lower energy barrier (0.141 vs 0.504 eV Bi). In situ ex characterizations reveal alloys solid‐solution process constrained by reconstructed Bi−S bonds after dealloying, realizing complete recovery crystalline phase to avoid migration aggregation Bi. Accordingly, delivers reversible 325 mAh g −1 at 1 C extraordinary ultrahigh‐rate stability 226 100 over 25 000 cycles. proposed mechanism induced mode modulation expected be conducive practical electrode design fast‐charging batteries.

Язык: Английский

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Cascade Dual Sites Modulate Local CO Coverage and Hydrogen-Binding Strength to Boost CO₂ Electroreduction to Ethylene

Journal of the American Chemical Society, Год журнала: 2024, Номер 146(8), С. 5693 - 5701

Опубликована: Фев. 9, 2024

Rationally modulating the binding strength of reaction intermediates on surface sites copper-based catalysts could facilitate C–C coupling to generate multicarbon products in an electrochemical CO2 reduction reaction. Herein, theoretical calculations reveal that cascade Ag–Cu dual synergistically increase local CO coverage and lower kinetic barrier for protonation, leading enhanced asymmetric C2H4. As a proof concept, Cu3N-Ag nanocubes (NCs) with Ag located partial Cu Cu3N unit center are successfully synthesized. The Faraday efficiency current density C2H4 over NCs 7.8 9.0 times those NCs, respectively. In situ spectroscopies combined confirm produce promote *COCHO, significantly enhancing generation Our work provides new insights into catalysis strategy at atomic scale boosting products.

Язык: Английский

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Atomically Precise Copper Nanoclusters for Highly Efficient Electroreduction of CO₂ towards Hydrocarbons via Breaking the Coordination Symmetry of Cu Site

Angewandte Chemie International Edition, Год журнала: 2023, Номер 62(36)

Опубликована: Июль 20, 2023

Abstract We propose an effective highest occupied d‐orbital modulation strategy engendered by breaking the coordination symmetry of sites in atomically precise Cu nanocluster (NC) to switch product CO 2 electroreduction from HCOOH/CO higher‐valued hydrocarbons. An well‐defined 6 NC with symmetry‐broken Cu−S N 1 active (named (MBD) , MBD=2‐mercaptobenzimidazole) was designed and synthesized a judicious choice ligand containing both S atoms. Different previously reported high HCOOH selectivity NCs 3 sites, structure shows Faradaic efficiency toward hydrocarbons 65.5 % at −1.4 V versus reversible hydrogen electrode (including 42.5 CH 4 23 C H ), partial current density −183.4 mA cm −2 . Theoretical calculations reveal that can rearrange 3d orbitals as d‐orbital, thus favoring generation key intermediate *COOH instead *OCHO favor *CO formation, followed hydrogenation and/or C−C coupling produce This is first attempt regulate mode atom for generation, provides new inspiration designing efficient RR towards highly‐valued products.

Язык: Английский

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Indium Cyanamide for Industrial-Grade CO₂ Electroreduction to Formic Acid

Journal of the American Chemical Society, Год журнала: 2023, Номер 145(25), С. 14101 - 14111

Опубликована: Июнь 15, 2023

Developing industrial-grade electroreduction of CO2 to produce formate (HCOO–)/formic acid (HCOOH) depends on highly active electrocatalysts. However, structural changes due the inevitable self-reduction catalysts result in severe long-term stability issues at current density. Herein, linear cyanamide anion ([NCN]2–)-constructed indium nanoparticles (InNCN) were investigated for reduction HCOO– with a Faradaic efficiency up 96% under partial density (jformate) 250 mA cm–2. Bulk electrolysis jformate 400 cm–2 requires only −0.72 VRHE applied potential iR correction. It also achieves continuous production pure HCOOH ∼125 160 h. The excellent activity and InNCN are attributed its unique features, including strongly σ-donating [NCN]2– ligands, transformation [N═C═N]2– [N≡C–N]2–, open framework structure. This study affirms metal cyanamides as promising novel materials electrocatalytic reduction, broadening variety understanding structure–activity relationships.

Язык: Английский

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MOF-based materials for electrochemical reduction of carbon dioxide

Coordination Chemistry Reviews, Год журнала: 2023, Номер 494, С. 215333 - 215333

Опубликована: Июль 28, 2023

Язык: Английский

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