Liquid Fluxional Ga Single Atom Catalysts for Efficient Electrochemical CO₂Reduction

Angewandte Chemie International Edition, Год журнала: 2022, Номер 62(3)

Опубликована: Ноя. 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.

Язык: Английский

---

Construction of Co₄ Atomic Clusters to Enable Fe−N₄ Motifs with Highly Active and Durable Oxygen Reduction Performance

Angewandte Chemie International Edition, Год журнала: 2023, Номер 62(30)

Опубликована: Май 24, 2023

Abstract Fe−N−C catalysts with single‐atom Fe−N 4 configurations are highly needed owing to the high activity for oxygen reduction reaction (ORR). However, limited intrinsic and dissatisfactory durability have significantly restrained practical application of proton‐exchange membrane fuel cells (PEMFCs). Here, we demonstrate that constructing adjacent metal atomic clusters (ACs) is effective in boosting ORR performance stability catalysts. The integration uniform Co ACs on N‐doped carbon substrate (Co @/Fe 1 @NC) realized through a “pre‐constrained” strategy using molecular Fe(acac) 3 implanted precursors. as‐developed @NC catalyst exhibits excellent half‐wave potential ( E 1/2 ) 0.835 V vs. RHE acidic media peak power density 840 mW cm −2 H 2 −O cell test. First‐principles calculations further clarify catalytic mechanism identified modified ACs. This work provides viable precisely establishing atomically dispersed polymetallic centers efficient energy‐related catalysis.

Язык: Английский

---

Phosphorus Tailors thed‐Band Center of Copper Atomic Sites for Efficient CO₂Photoreduction under Visible‐Light Irradiation

Angewandte Chemie International Edition, Год журнала: 2022, Номер 61(38)

Опубликована: Июль 8, 2022

Photoreduction of CO2 into solar fuels has received great interest, but suffers from low catalytic efficiency and poor selectivity. Herein, two single-Cu-atom catalysts with unique Cu configurations in phosphorus-doped carbon nitride (PCN), namely, Cu1 N3 @PCN P3 were fabricated via selective phosphidation, tested visible light-driven reduction by H2 O without sacrificial agents. was exclusively active for CO production a rate 49.8 μmolCO gcat-1 h-1 , outperforming most polymeric (C3 N4 ) based catalysts, while preferably yielded . Experimental theoretical analysis suggested that doping P C3 replacing corner C atom upshifted the d-band center close to Fermi level, which boosted adsorption activation on making efficiently convert CO. In contrast, much lower 3d electron energy exhibited negligible adsorption, thereby preferring formation photocatalytic splitting.

Язык: Английский

---

Single-Atom Yttrium Engineering Janus Electrode for Rechargeable Na–S Batteries

Journal of the American Chemical Society, Год журнала: 2022, Номер 144(41), С. 18995 - 19007

Опубликована: Окт. 10, 2022

The development of rechargeable Na-S batteries is very promising, thanks to their considerably high energy density, abundance elements, and low costs yet faces the issues sluggish redox kinetics S species polysulfide shuttle effect as well Na dendrite growth. Following theory-guided prediction, rare-earth metal yttrium (Y)-N4 unit has been screened a favorable Janus site for chemical affinity polysulfides electrocatalytic conversion, reversible uniform deposition. To this end, we adopt metal-organic framework (MOF) prepare single-atom hybrid with Y single atoms being incorporated into nitrogen-doped rhombododecahedron carbon host (Y SAs/NC), which features properties sodiophilicity sulfiphilicity thus presents highly desired electrochemical performance when used sodium anode sulfur cathode full cell. Impressively, cell capable delivering capacity 822 mAh g-1 shows superdurable cyclability (97.5% retention over 1000 cycles at current density 5 A g-1). proof-of-concept three-dimensional (3D) printed pouch validate potential practical applications such batteries, shedding light on promising cells future application in storage or power batteries.

Язык: Английский

---

Tuning Mass Transport in Electrocatalysis Down to Sub‐5 nm through Nanoscale Grade Separation

Angewandte Chemie International Edition, Год журнала: 2022, Номер 62(3)

Опубликована: Ноя. 18, 2022

Nano and single-atom catalysis open new possibilities of producing green hydrogen (H2 ) by water electrolysis. However, for the evolution reaction (HER) which occurs at a characteristic rate proportional to potential, fast generation H2 nanobubbles atomic-scale interfaces often leads blockage active sites. Herein, nanoscale grade-separation strategy is proposed tackle mass-transport problem utilizing ordered three-dimensional (3d) interconnected sub-5 nm pores. The results reveal that 3d criss-crossing mesopores with grade separation allow efficient diffusion bubbles along channels. After support ultrafine ruthenium (Ru), are on superior level two-dimensional system maximizing catalyst performance obtained Ru outperforms most other HER catalysts. This work provides potential route fine-tuning few-nanometer mass transport during

Язык: Английский

---

A strongly coupled Ru–CrOx cluster–cluster heterostructure for efficient alkaline hydrogen electrocatalysis

Nature Catalysis, Год журнала: 2024, Номер 7(4), С. 441 - 451

Опубликована: Март 11, 2024

Язык: Английский

---

Atomically Dispersed Au-Assisted C–C Coupling on Red Phosphorus for CO₂ Photoreduction to C₂H₆

Journal of the American Chemical Society, Год журнала: 2022, Номер 144(48), С. 22075 - 22082

Опубликована: Ноя. 22, 2022

Single-atom catalysts have exhibited great potential in the photocatalytic conversion of CO2 to C2 products, but generation gaseous multi-carbon hydrocarbon products is still challenging. Previously, supports a single atom consist multiple elements, making C-C coupling difficult because coordination environment single-atom sites diversified and control. Here, we steer by implanting an Au on red phosphorus (Au1/RP), support with uniform structure composed element, lower electronegativity, better ability absorb CO2. The electron-rich atoms near can function as active for activation. effectively reduce energy barrier coupling, boosting reaction kinetics formation C2H6. Notably, C2H6 selectivity turnover frequency Au1/RP reach 96% 7.39 h-1 without sacrificial agent, respectively, which almost represents best photocatalyst chemical synthesis date. This research will provide new ideas design high-efficiency photocatalysts products.

Язык: Английский

---

Engineering Water Molecules Activation Center on Multisite Electrocatalysts for Enhanced CO₂ Methanation

Journal of the American Chemical Society, Год журнала: 2022, Номер 144(28), С. 12807 - 12815

Опубликована: Июль 5, 2022

The renewable energy-powered electrolytic reduction of carbon dioxide (CO2) to methane (CH4) using water as a reaction medium is one the most promising paths store intermittent energy and address global sustainability problems. However, role in electrolyte often overlooked. In particular, slow dissociation kinetics limits proton-feeding rate, which severely damages selectivity activity methanation process involving multiple electrons protons transfer. Here, we present novel tandem catalyst comprising Ir single-atom (Ir1)-doped hybrid Cu3N/Cu2O multisite that operates efficiently converting CO2 CH4. Experimental theoretical calculation results reveal Ir1 facilitates into proton feeds sites for *CO protonation pathway toward *CHO. displays high Faradaic efficiency 75% CH4 with current density 320 mA cm-2 flow cell. This work provides strategy rational design high-efficiency catalytic systems.

Язык: Английский

---

Regulating the FeN₄ Moiety by Constructing Fe–Mo Dual-Metal Atom Sites for Efficient Electrochemical Oxygen Reduction

Nano Letters, Год журнала: 2022, Номер 22(23), С. 9507 - 9515

Опубликована: Ноя. 15, 2022

An Fe–N–C catalyst with an FeN4 active moiety has gained ever-increasing attention for the oxygen reduction reaction (ORR); however, catalytic performance is sluggish in acidic solutions and regulation still a challenge. Herein, Fe–Mo dual-metal sites were constructed to tune ORR activity of mononuclear Fe site embedded porous nitrogen-doped carbon. The cracking O–O bonds much more facile on atomic pair due preferred bridge-cis adsorption model molecules. downshift d band center when Mo atom introduced FeNx configuration optimizes absorption–desorption behavior intermediates FeMoN6 moiety, thus boosting performance. construction regulate catalytically paves way electrocatalytic other similar non-precious-metal catalysts.

Язык: Английский

---

Co-catalytic metal–support interactions in single-atom electrocatalysts

Nature Reviews Materials, Год журнала: 2024, Номер 9(3), С. 173 - 189

Опубликована: Янв. 10, 2024

Язык: Английский

---