Isolated Cu Sites in CdS Hollow Nanocubes with Doping-Location-Dependent Performance for Photocatalytic CO₂ Reduction

ACS Catalysis, Год журнала: 2024, Номер 14(3), С. 1468 - 1479

Опубликована: Янв. 13, 2024

Doping engineering has enabled the construction of homogeneous and abundant atomic-level catalytic sites for photocatalytic CO2 reduction with improved selectivity target product. However, little is known about effect spatial position heteroatoms on activity semiconductors toward reduction. Herein, uniform Cu doping into bulk phase hollow CdS cubes (HCC) onto surface HCC, denoted as Cu/HCC HCC@Cu, respectively, are prepared by tuning introduction order sources. Experimental analysis shows that both methods can promote separation migration photoinduced charge carriers in CdS. Notably, HCC@Cu leads to much better proton H2 production performance but lower efficiency compared bare In sharp contrast, enhances CO2-to-CO conversion while mitigating evolution. This should be ascribed smaller overpotential saturated system than Ar system. addition, atoms shifts d band center upward near Fermi energy level, which promotes adsorption activation These results indicate photoelectrons a prolonged lifetime preferably reduce molecules rather protons. The density functional theory (DFT) calculation show desorption CO*, adaptable sulfur vacancies (Vs) produced situ techniques stimulate formation CO* intermediates, resulting high CO. work reveals different heteroatom locations will provide reference design efficient photocatalysts fine structure.

Язык: Английский

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Solar-driven sugar production directly from CO2 via a customizable electrocatalytic–biocatalytic flow system

Nature Communications, Год журнала: 2024, Номер 15(1)

Опубликована: Март 25, 2024

Abstract Conventional food production is restricted by energy conversion efficiency of natural photosynthesis and demand for resources. Solar-driven artificial synthesis from CO 2 provides an intriguing approach to overcome the limitations while promoting carbon-neutral economy, however, it remains very challenging. Here, we report design a hybrid electrocatalytic−biocatalytic flow system, coupling photovoltaics-powered electrocatalysis (CO formate) with five-enzyme cascade platform (formate sugar) engineered via genetic mutation bioinformatics, which achieves C 6 sugar (L-sorbose) solar-to-food 3.5%, outperforming over three-fold. This system can in principle be programmed diverse enzymes toward multifarious . work opens promising avenue under confined environments.

Язык: Английский

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Challenges and Prospects in the Catalytic Conversion of Carbon Dioxide to Formaldehyde

Angewandte Chemie International Edition, Год журнала: 2022, Номер 61(46)

Опубликована: Сен. 6, 2022

Formaldehyde (HCHO) is a crucial C

Язык: Английский

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High entropy materials frontier and theoretical insights for logistics CO2 reduction and hydrogenation: Electrocatalysis, photocatalysis and thermo-catalysis

Journal of Alloys and Compounds, Год журнала: 2023, Номер 969, С. 172232 - 172232

Опубликована: Сен. 20, 2023

Язык: Английский

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Donor‐Acceptor Activation of Carbon Dioxide

Chemistry - A European Journal, Год журнала: 2023, Номер 29(61)

Опубликована: Июль 26, 2023

Abstract The activation and functionalization of carbon dioxide entails great interest related to its abundance, low toxicity associated environmental problems. However, the inertness CO 2 has posed a challenge towards efficient conversion added‐value products. In this review we discuss one strategies that have been widely used capture activate dioxide, namely use donor‐acceptor interactions by partnering Lewis acidic basic fragment. This type resembles found in metalloenzymes, whose outstanding performance catalytically transforming encourages further bioinspired research. We divided into three general sections based on nature active sites: metal‐free examples (mainly formed frustrated pairs), main group‐transition metal combinations, transition heterobimetallic complexes. Overall, hundred compounds cooperatively interactions, revealing wide range structural motifs.

Язык: Английский

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Rational Design of Heterogeneous Dual-Atom Catalysts for CO₂ Electroreduction Reactions

ACS Applied Energy Materials, Год журнала: 2023, Номер 6(13), С. 6851 - 6882

Опубликована: Июнь 23, 2023

One of the strategies to mitigate concentration CO2 in atmosphere and reduce global warming effect is capture convert it synthetic fuels fine chemicals. Although structurally chemically stable, electrochemical transformation has attracted much attention because offers mild reaction conditions regarding temperature, pressure, process controllability. Among various electrocatalysts, dual-atom catalysts (DACs) have been extensively developed past few years due their unique features for reactions small molecules. The catalytic activity DACs reduction (eCO2RR) surpassed single-atom (SACs) by providing a higher metal loading, two active sites (cf. one site SACs), synergistic adjacent atoms, possibility tuning electronic state (adjusting d-band center), more possible configuration modes (side-on side-bridge) adsorption only end-on end-bridge SACs). As result, both reactivity selectivity eCO2RR can be achieved breaking scaling relationships with interactions between intermediates sites. This review highlights discusses recent progress applying homo- heteronuclear focusing on synthesis, characterization, performance.

Язык: Английский

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The CO₂ Tree: The Potential for Carbon Dioxide Utilization Pathways

ACS Sustainable Chemistry & Engineering, Год журнала: 2024, Номер 13(1), С. 5 - 29

Опубликована: Дек. 13, 2024

Among the most active areas of chemistry research today is that carbon dioxide utilization: an area was viewed as futile and commercially impractical not so long ago due to energetic stability CO2 molecule. The breakthroughs largely began in earnest 1990s have accelerated now make up a diverse plentiful portfolio technological scientific advances commercialized technologies. Here, "The Tree" presented tool illustrate breadth potential products from utilization communicate these chemical address greatest challenge society faces today: climate change. It intended be useful for scientists, engineers, legislators, advocates, industrial decision-makers, policy makers, general public know what already possible may near future.

Язык: Английский

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Molecular Electrochemical Catalysis of CO-to-Formaldehyde Conversion with a Cobalt Complex

Journal of the American Chemical Society, Год журнала: 2024, Номер 146(32), С. 22129 - 22133

Опубликована: Июль 31, 2024

Formox, a highly energy-intensive process, currently serves as the primary source of formaldehyde (HCHO), for which there is crucial and steadily growing chemical demand. The alternative electrochemical production HCHO from C1 carbon sources such CO2 CO still in its early stages, with even few identified cases lacking mechanistic rationalization. In this study, we demonstrate that cobalt phthalocyanine (CoPc) immobilized on multiwalled nanotubes (MW-CNTs) constitutes an excellent electrocatalytic system producing productivity through direct reduction CO, two-electron product CO2. By carefully adjusting both pH applied potential, conditions enable partial current density 0.64 mA cm–2 (17.5% Faradaic efficiency, FE) total FE 61.2% liquid products (formaldehyde methanol). A mechanism proposed.

Язык: Английский

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Fundamental Insights into Photoelectrochemical Carbon Dioxide Reduction: Elucidating the Reaction Pathways

ACS Catalysis, Год журнала: 2024, Номер 14(22), С. 16795 - 16833

Опубликована: Окт. 31, 2024

The photoelectrochemical (PEC) reduction of carbon dioxide (CO2) to produce solar fuels presents a sustainable strategy mitigate CO2 emissions and alleviate the global energy crisis. While significant research efforts have been dedicated optimizing cell system configurations designing efficient photoelectrocatalysts, there remains lack in-depth understanding pathway. This review provides comprehensive overview fundamental insights PEC with focus on pathways from perspectives final products adsorption modes. First, key challenges are identified analyzed, including initial activation CO2, competitive hydrogen evolution reaction (HER), complex carbon–carbon (C–C) coupling process. then examines aspects process, covering state-of-the-art devices, their operational principles, methodologies for capturing intermediates. through concerted or sequential proton–electron transfer mechanisms is discussed in detail. Furthermore, potential systematically categorized basis distinct modes that drive insertion, carbon-coordinated oxygen-coordinated monodentate adsorption, bidentate oxygen vacancies. Detailed leading formation C1, C2, C3 compounds elucidated, an emphasis strategies enhance selectivity toward C1 C2+ products. In particular, aids catalyst design. For production, design focuses promoting activation, as rate-determining step (RDS) activation. contrast, formation, aim increase intermediate concentration, thereby enhancing lateral interaction intermediates, which crucial C–C coupling. Finally, summarizes future breakthroughs electron, interfacial, ionic pathways, offering into ongoing technologies.

Язык: Английский

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Theory-guided development of homogeneous catalysts for the reduction of CO₂to formate, formaldehyde, and methanol derivatives

Chemical Science, Год журнала: 2023, Номер 14(11), С. 2799 - 2807

Опубликована: Янв. 1, 2023

Computational volcano plots are used to predict selectivity in the context of (first-row) transition metal-catalyzed CO 2 reduction. The expected trends were tested experimentally and allowed for systematic improvement catalyst.

Язык: Английский

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