P and Cu Dual Sites on Graphitic Carbon Nitride for Photocatalytic CO₂Reduction to Hydrocarbon Fuels with High C₂H₆Evolution

Angewandte Chemie International Edition, Год журнала: 2022, Номер 61(40)

Опубликована: Авг. 15, 2022

The light-driven CO2 reduction to multi-carbon products is especially meaningful, while the low efficiency of multi-electron transfer and sluggish C-C coupling greatly hinder its development. Herein, we report a photocatalyst comprising P Cu dual sites anchored on graphitic carbon nitride (P/Cu SAs@CN), which achieves high C2 H6 evolution rate 616.6 μmol g-1 h-1 in reducing hydrocarbons. detailed spectroscopic characterizations identify formation charge-enriched sites, where isolated atoms serve as hole capture during photocatalysis. Theoretical simulations combined with situ FTIR measurement reveal kinetically feasible process for intermediate (*OC-COH) confirm favorable production P/Cu SAs@CN photocatalyst. This work offers new insights into design atomic precision toward highly efficient photocatalytic conversion value-added products.

Язык: Английский

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Atomically dispersed materials: Ideal catalysts in atomic era

Nano Research, Год журнала: 2023, Номер 17(1), С. 18 - 38

Опубликована: Май 25, 2023

Язык: Английский

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Coordination Symmetry Breaking of Single‐Atom Catalysts for Robust and Efficient Nitrate Electroreduction to Ammonia

Advanced Materials, Год журнала: 2022, Номер 34(36)

Опубликована: Июль 16, 2022

Nitrate electrocatalytic reduction (NO3 RR) for ammonia production is a promising strategy to close the N-cycle from nitration contamination, as well an alternative Haber-Bosch process with less energy consumption and carbon dioxide release. However, current long-term stability of NO3 RR catalysts usually tens hours, far requirements industrialization. Here, symmetry-broken Cusingle-atom are designed, catalytic activity retained after operation more than 2000 h, while average rate 27.84 mg h-1 cm-2 at industrial level density 366 mA achieved, obtaining good balance between stability. Coordination symmetry breaking achieved by embedding one Cu atom in graphene nanosheets two N O atoms cis-configuration, effectively lowering coordination symmetry, rendering active site polar, accumulating NO3- near electrocatalyst surface. Additionally, cis-coordination splits 3d orbitals, which generates orbital-symmetry-matched π-complex key intermediate *ONH reduces barrier, compared σ-complex generated other catalysts. These results reveal critical role single-atom catalysts, prompting design coordination-symmetry-broken electrocatalysts toward possible

Язык: Английский

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Long‐Range Interactions in Diatomic Catalysts Boosting Electrocatalysis

Angewandte Chemie International Edition, Год журнала: 2022, Номер 61(52)

Опубликована: Окт. 6, 2022

Abstract The simultaneous presence of two active metal centres in diatomic catalysts (DACs) leads to the occurrence specific interactions between sites. Such interactions, referred as long‐range (LRIs), play an important role determining rate and selectivity a reaction. optimal combination must be determined achieve targeted efficiency. To date, various types DACs have been synthesised applied electrochemistry. However, LRIs not systematically summarised. Herein, regulation, mechanism, electrocatalytic applications are comprehensively summarised discussed. In addition basic information above, challenges, opportunities, future development proposed order present overall view reference for research.

Язык: Английский

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Synergistic Fe−Se Atom Pairs as Bifunctional Oxygen Electrocatalysts Boost Low‐Temperature Rechargeable Zn‐Air Battery

Angewandte Chemie International Edition, Год журнала: 2023, Номер 62(15)

Опубликована: Фев. 18, 2023

Herein, we successfully construct bifunctional electrocatalysts by synthesizing atomically dispersed Fe-Se atom pairs supported on N-doped carbon (Fe-Se/NC). The obtained Fe-Se/NC shows a noteworthy oxygen catalytic performance with low potential difference of 0.698 V, far superior to that reported Fe-based single-atom catalysts. theoretical calculations reveal p-d orbital hybridization around the leads remarkably asymmetrical polarized charge distributions. based solid-state rechargeable Zn-air batteries (ZABs-Fe-Se/NC) present stable charge/discharge 200 h (1090 cycles) at 20 mA cm-2 25 °C, which is 6.9 times ZABs-Pt/C+Ir/C. At extremely temperature -40 ZABs-Fe-Se/NC displays an ultra-robust cycling 741 (4041 1 , about 11.7 More importantly, could be operated for 133 (725 even 5 °C.

Язык: Английский

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Dual‐Atom Support Boosts Nickel‐Catalyzed Urea Electrooxidation

Angewandte Chemie International Edition, Год журнала: 2023, Номер 62(22)

Опубликована: Март 24, 2023

Nickel-based catalysts have been regarded as one of the most promising electrocatalysts for urea oxidation reaction (UOR), however, their activity is largely limited by inevitable self-oxidation Ni species (NSOR) during UOR. Here, we proposed an interface chemistry modulation strategy to trigger occurrence UOR before NSOR via constructing a 2D/2D heterostructure that consists ultrathin NiO anchored Ru-Co dual-atom support (Ru-Co DAS/NiO). Operando spectroscopic characterizations confirm this unique triggering mechanism on surface DAS/NiO. Consequently, fabricated catalyst exhibits outstanding with low potential 1.288 V at 10 mA cm-2 and remarkable long-term durability more than 330 h operation. DFT calculations demonstrate favorable electronic structure induced heterointerface endows energetically NSOR.

Язык: Английский

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Lattice Strain and Schottky Junction Dual Regulation Boosts Ultrafine Ruthenium Nanoparticles Anchored on a N-Modified Carbon Catalyst for H₂ Production

Journal of the American Chemical Society, Год журнала: 2022, Номер 144(42), С. 19619 - 19626

Опубликована: Окт. 12, 2022

Ruthenium-based materials are considered great promising candidates to replace Pt-based catalysts for hydrogen production in alkaline conditions. Herein, we adopt a facile method rationally design neoteric Schottky catalyst which uniform ultrafine ruthenium nanoparticles featuring lattice compressive stress supported on nitrogen-modified carbon nanosheets (Ru NPs/NC) efficient evolution reaction (HER). Lattice strain and junction dual regulation ensures that the Ru NPs/NC with an appropriate nitrogen content displays superb H2 media. Particularly, NPs/NC-900 1.3% attractive activity durability HER low overpotential of 19 mV at 10 mA cm-2 1.0 M KOH electrolyte. The situ X-ray absorption fine structure measurements indicate low-valence nanoparticle shrinking Ru-Ru bond acts as catalytic active site during process. Furthermore, multiple spectroscopy analysis density functional theory calculations demonstrate tunes electron adsorption center, thus enhancing activity. This strategy provides novel concept advanced electrocatalysts production.

Язык: Английский

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Microenvironment Engineering of Single/Dual‐Atom Catalysts for Electrocatalytic Application

Advanced Materials, Год журнала: 2023, Номер 35(31)

Опубликована: Фев. 23, 2023

Single/dual-metal atoms supported on carbon matrix can be modulated by coordination structure and neighboring active sites. Precisely designing the geometric electronic uncovering structure-property relationships of single/dual-metal confront with grand challenges. Herein, this review summarizes latest progress in microenvironment engineering single/dual-atom sites via a comprehensive comparison single-atom catalyst (SACs) dual-atom catalysts (DACs) term design principles, modulation strategy, theoretical understanding structure-performance correlations. Subsequently, recent advances several typical electrocatalysis process are discussed to get general reaction mechanisms finely-tuned SACs DACs. Finally, full-scaled summaries challenges prospects given for This will provide new inspiration development atomically dispersed electrocatalytic application.

Язык: Английский

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The reformation of catalyst: From a trial-and-error synthesis to rational design

Nano Research, Год журнала: 2023, Номер 17(4), С. 3261 - 3301

Опубликована: Сен. 27, 2023

Язык: Английский

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Toward Electrocatalytic Methanol Oxidation Reaction: Longstanding Debates and Emerging Catalysts

Advanced Materials, Год журнала: 2023, Номер 35(26)

Опубликована: Янв. 27, 2023

The study of direct methanol fuel cells (DMFCs) has lasted around 70 years, since the first investigation in early 1950s. Though enormous effort been devoted this field, it is still far from commercialization. oxidation reaction (MOR), as a semi-reaction DMFCs, bottleneck that restricts overall performance DMFCs. To date, there intense debate on complex six-electron reaction, but barely any reviews have systematically discussed topic. end, controversies and progress regarding electrocatalytic mechanisms, evaluations well design science toward MOR electrocatalysts are summarized. This review also provides comprehensive introduction recent development emerging with focus innovation alloy, core-shell structure, heterostructure, single-atom catalysts. Finally, perspectives future outlook mechanisms provided.

Язык: Английский

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