Atomically dispersed materials: Ideal catalysts in atomic era

Nano Research, Journal Year: 2023, Volume and Issue: 17(1), P. 18 - 38

Published: May 25, 2023

Language: Английский

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Isolating Single and Few Atoms for Enhanced Catalysis

Advanced Materials, Journal Year: 2022, Volume and Issue: 34(39)

Published: May 17, 2022

Abstract Atomically dispersed metal catalysts have triggered great interest in the field of catalysis owing to their unique features. Isolated single or few atoms can be anchored on substrates via chemical bonding space confinement maximize atom utilization efficiency. The key challenge lies precisely regulating geometric and electronic structure active centers, thus significantly influencing catalytic properties. Although several reviews been published preparation, characterization, application single‐atom (SACs), comprehensive understanding SACs, dual‐atom (DACs), atomic clusters has never systematically summarized. Here, recent advances engineering local environments state‐of‐the‐art DACs, for enhanced performance are highlighted. Firstly, various synthesis approaches presented. Then, special attention is focused elucidation terms state coordination structure. Furthermore, a summary isolated applications thermocatalysis, electrocatalysis, photocatalysis provided. Finally, potential challenges future opportunities this emerging This review will pave way regulate microenvironment site boosting processes.

Language: Английский

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Liquid Fluxional Ga Single Atom Catalysts for Efficient Electrochemical CO₂Reduction

Angewandte Chemie International Edition, Journal Year: 2022, Volume and Issue: 62(3)

Published: Nov. 18, 2022

Precise design and tuning of the micro-atomic structure single atom catalysts (SACs) can help efficiently adapt complex catalytic systems. Herein, we inventively found that when active center main group element gallium (Ga) is downsized to atomic level, whose characteristic has significant differences from conventional bulk rigid Ga catalysts. The SACs with a P, S coordination environment display specific flow properties, showing CO products FE ≈92 % at -0.3 V vs. RHE in electrochemical CO2 reduction (CO2 RR). Theoretical simulations demonstrate adaptive dynamic transition optimizes adsorption energy *COOH intermediate renews sites time, leading excellent RR selectivity stability. This liquid system interfaces lays foundation for future exploration synthesis catalysis.

Language: Английский

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Halogen‐Incorporated Sn Catalysts for Selective Electrochemical CO2 Reduction to Formate

Angewandte Chemie International Edition, Journal Year: 2022, Volume and Issue: 62(10)

Published: Dec. 23, 2022

Electrochemically reducing CO2 to valuable fuels or feedstocks is recognized as a promising strategy simultaneously tackle the crises of fossil fuel shortage and carbon emission. Sn-based catalysts have been widely studied for electrochemical reduction reaction (CO2 RR) make formic acid/formate, which unfortunately still suffer from low activity, selectivity stability. In this work, halogen (F, Cl, Br I) was introduced into Sn catalyst by facile hydrolysis method. The presence confirmed collection ex situ in characterizations, rendered more positive valence state halogen-incorporated compared unmodified under cathodic potentials RR therefore tuned adsorption strength key intermediate (*OCHO) toward formate formation. As result, exhibited greatly enhanced catalytic performance produce formate.

Language: Английский

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Progress in regulating electronic structure strategies on Cu-based bimetallic catalysts for CO2 reduction reaction

Advanced Powder Materials, Journal Year: 2022, Volume and Issue: 1(4), P. 100055 - 100055

Published: May 5, 2022

To address the ever-increasing CO2 concentration problem in atmospheric air arisen by massive consumption of fossil fuels, electrocatalytic technologies that reduce to generate high value-added products have been gaining increasing interest. Cu-based reduction catalysts attracted widespread attention owing their capability generating C1 and C2+ products. However, are highly challenged low product selectivity. Recently, bimetallic found unique catalytical activity selectivity reactions (CO2RR). The incorporation other metals can change electronic circumstance catalysts, promoting adsorption ability intermediate consequently leading In this minireview, we intend summarize recent advances producing products, involving designing heterostructure, alloy, defects surface modification engineering. We pay special regulation structure composite as well insights into relationship between property performance for catalysts.

Language: Английский

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Sn Dopants with Synergistic Oxygen Vacancies Boost CO₂ Electroreduction on CuO Nanosheets to CO at Low Overpotential

ACS Nano, Journal Year: 2022, Volume and Issue: 16(11), P. 19210 - 19219

Published: Oct. 18, 2022

Using the electrochemical CO2 reduction reaction (CO2RR) with Cu-based electrocatalysts to achieve carbon-neutral cycles remains a significant challenge because of its low selectivity and poor stability. Modulating surface electron distribution by defects engineering or doping can effectively improve CO2RR performance. Herein, we synthesize electrocatalyst Vo-CuO(Sn) nanosheets containing oxygen vacancies Sn dopants for application in CO2RR-to-CO. Density functional theory calculations confirm that incorporation atoms substantially reduces energy barrier *COOH *CO intermediate formation, which results high efficiency, overpotential, superior stability CO conversion. This possesses Faraday efficiency (FE) 99.9% at overpotential 420 mV partial current density up 35.22 mA cm-2 -1.03 V versus reversible hydrogen electrode (RHE). The FECO could retain over 95% within wide potential area from -0.48 -0.93 RHE. Moreover, obtain long-term more than 180 h only slight decay activity. Therefore, this work provides an effective route designing environmentally friendly

Language: Английский

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Enhancing Selective Electrochemical CO₂ Reduction by In Situ Constructing Tensile-Strained Cu Catalysts

ACS Catalysis, Journal Year: 2023, Volume and Issue: 13(7), P. 4711 - 4718

Published: March 23, 2023

Heteroatom-doped Cu-based catalysts have been found to show not only enhanced activity of electrochemical CO2 reduction reaction (CO2RR) but also the possibility tune selectivity CO2RR. However, complex and variable nature materials renders it difficult elucidate origin improved performance, which further hinders rational design catalysts. Here, we demonstrate that CO2RR can be tuned by manipulating lattice strain The combined operando ex situ spectroscopic characterizations reveal initial compressively strained Sn-doped CuO could converted tensile-strained Sn/Cu alloy under conditions. In attenuated total reflectance surface-enhanced infrared absorption spectroscopy (ATR-SEITAS) theoretical calculations favor CO formation due preponderant adsorption *CO much lower free energies *COOH, thus effectively suppressing dimerization process production HCOOH H2. This work provides a strategy performance strain.

Language: Английский

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Dual-site catalysts featuring platinum-group-metal atoms on copper shapes boost hydrocarbon formations in electrocatalytic CO2 reduction

Nature Communications, Journal Year: 2023, Volume and Issue: 14(1)

Published: May 27, 2023

Copper-based catalyst is uniquely positioned to catalyze the hydrocarbon formations through electrochemical CO2 reduction. The design freedom limited for alloying copper with H-affinitive elements represented by platinum group metals because latter would easily drive hydrogen evolution reaction override We report an adept of anchoring atomically dispersed metal species on both polycrystalline and shape-controlled Cu catalysts, which now promote targeted reduction while frustrating undesired reaction. Notably, alloys similar formulations but comprising small or palladium clusters fail this objective. With appreciable amount CO-Pd1 moieties surfaces, facile CO* hydrogenation CHO* CO-CHO* coupling viable as one main pathways Cu(111) Cu(100) selectively produce CH4 C2H4 Pd-Cu dual-site pathways. work broadens choices in aqueous phases.

Language: Английский

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Electrocatalyst Microenvironment Engineering for Enhanced Product Selectivity in Carbon Dioxide and Nitrogen Reduction Reactions

ACS Catalysis, Journal Year: 2023, Volume and Issue: 13(8), P. 5375 - 5396

Published: April 6, 2023

Carbon and nitrogen fixation strategies are regarded as alternative routes to produce valuable chemicals used energy carriers fertilizers that traditionally obtained from unsustainable energy-intensive coal gasification (CO CH4), Fischer–Tropsch (C2H4), Haber–Bosch (NH3) processes. Recently, the electrocatalytic CO2 reduction reaction (CO2RR) N2 (NRR) have received tremendous attention, with merits of being both efficient store renewable electricity while providing preparation fossil-fuel-driven reactions. To date, development CO2RR NRR processes is primarily hindered by competitive hydrogen evolution (HER); however, corresponding for inhibiting this undesired side still quite limited. Considering such complex reactions involve three gas–liquid–solid phases successive proton-coupled electron transfers, it appears meaningful review current improving product selectivity in light their respective mechanisms, kinetics, thermodynamics. By examining developments understanding catalyst design, electrolyte engineering, three-phase interface modulation, we discuss key NRR: (i) targeting molecularly defined active sites, (ii) increasing local reactant concentration at (iii) stabilizing confining intermediates.

Language: Английский

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Tuning C1/C2 Selectivity of CO2 Electrochemical Reduction over in‐Situ Evolved CuO/SnO2 Heterostructure

Angewandte Chemie International Edition, Journal Year: 2023, Volume and Issue: 62(40)

Published: July 24, 2023

Abstract Heterostructured oxides with versatile active sites, as a class of efficient catalysts for CO 2 electrochemical reduction (CO ER), are prone to undergo structure reconstruction under working conditions, thus bringing challenges understanding the reaction mechanism and rationally designing catalysts. Herein, we first time elucidate structural CuO/SnO potentials reveal intrinsic relationship between ER product selectivity in situ evolved heterostructures. At −0.85 V RHE , evolves Cu O/SnO high HCOOH (Faradaic efficiency 54.81 %). Mostly interestingly, it is reconstructed Cu/SnO 2‐x at −1.05 significantly improved Faradaic ethanol 39.8 %. In Raman spectra density functional theory (DFT) calculations that synergetic absorption *COOH *CHOCO intermediates interface favors formation *CO decreases energy barrier C−C coupling, leading ethanol.

Language: Английский

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