Understanding the structure-performance relationship of active sites at atomic scale

Nano Research, Journal Year: 2022, Volume and Issue: 15(8), P. 6888 - 6923

Published: June 14, 2022

Language: Английский

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Engineering Single-Atom Active Sites on Covalent Organic Frameworks for Boosting CO₂ Photoreduction

Journal of the American Chemical Society, Journal Year: 2022, Volume and Issue: 144(37), P. 17097 - 17109

Published: Sept. 6, 2022

Solar carbon dioxide (CO2) conversion is an emerging solution to meet the challenges of sustainable energy systems and environmental/climate concerns. However, construction isolated active sites not only influences catalytic activity but also limits understanding structure-catalyst relationship CO2 reduction. Herein, we develop a universal synthetic protocol fabricate different single-atom metal (e.g., Fe, Co, Ni, Zn, Cu, Mn, Ru) anchored on triazine-based covalent organic framework (SAS/Tr-COF) backbone with bridging structure metal-nitrogen-chlorine for high-performance Remarkably, as-synthesized Fe SAS/Tr-COF as representative catalyst achieved impressive CO generation rate high 980.3 μmol g-1 h-1 selectivity 96.4%, over approximately 26 times higher than that pristine Tr-COF under visible light irradiation. From X-ray absorption fine analysis density functional theory calculations, superior photocatalytic performance attributed synergic effect atomically dispersed host, decreasing reaction barriers formation *COOH intermediates promoting adsorption activation well desorption. This work affords rational design state-of-the-art catalysts at molecular level provides in-depth insights efficient conversion.

Language: Английский

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Surface Activation and Ni‐S Stabilization in NiO/NiS₂for Efficient Oxygen Evolution Reaction

Angewandte Chemie International Edition, Journal Year: 2022, Volume and Issue: 61(35)

Published: June 22, 2022

Manipulating the active species and improving structural stabilization of sulfur-containing catalysts during OER process remain a tremendous challenge. Herein, we constructed NiO/NiS2 Fe-NiO/NiS2 as catalyst models to study effect Fe doping. As expected, exhibits low overpotential 270 mV at 10 mA cm-2 . The accumulation hydroxyl groups on surface materials after doping can promote formation highly NiOOH lower potential. Moreover, investigated level corrosion M-S bonds compared stability variation with different locations. Interestingly, bonded S in bulk sacrificial agent alleviate oxidation partial Ni-S thus endow long-term durability. This work could motivate community focus more resolving materials.

Language: Английский

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Sustainable zinc–air battery chemistry: advances, challenges and prospects

Chemical Society Reviews, Journal Year: 2023, Volume and Issue: 52(17), P. 6139 - 6190

Published: Jan. 1, 2023

Sustainable zinc-air batteries (ZABs) are considered promising energy storage devices owing to their inherent safety, high density, wide operating temperature window, environmental friendliness, etc., showing great prospect for future large-scale applications. Thus, tremendous efforts have been devoted addressing the critical challenges associated with sustainable ZABs, aiming significantly improve efficiency and prolong operation lifespan. The growing interest in ZABs requires in-depth research on oxygen electrocatalysts, electrolytes, Zn anodes, which not systematically reviewed date. In this review, fundamentals of electrocatalysts air cathodes, physicochemical properties ZAB issues strategies stabilization anodes summarized from perspective fundamental characteristics design principles. Meanwhile, significant advances situ/operando characterization highlighted provide insights into reaction mechanism dynamic evolution electrolyte|electrode interface. Finally, several thoughts perspectives provided regarding opportunities ZABs. Therefore, review provides a thorough understanding advanced chemistry, hoping that timely comprehensive can shed light upcoming horizons prosperous area.

Language: Английский

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Tailoring the d‐Orbital Splitting Manner of Single Atomic Sites for Enhanced Oxygen Reduction

Advanced Materials, Journal Year: 2023, Volume and Issue: 35(14)

Published: Feb. 11, 2023

Regulating the electronic states of single atomic sites around Fermi level remains a major concern for boosting electrocatalytic oxygen reduction reaction (ORR). Herein, Fe d-orbital splitting manner modulation strategy by constructing axial coordination on FeN4 is presented. Experimental investigations and theoretical calculations reveal that tractions induce distortion square-planar field (FeN4 SP), up to quasi-octahedral O1 OCquasi ), thus leading electron rearrangement with diluted spin polarization. The declined population unpaired electrons in dz2 , dxz dyz engenders moderate adsorption ORR intermediates, thereby reinforcing intrinsic activity. In situ infrared spectroscopy further demonstrates reordering occupation facilitates desorption *OH. exhibits dramatic improvement kinetic current density turnover frequency, which are fivefold tenfold higher than those SP. This work presents novel understanding improving performance through orbital-scale manipulation.

Language: Английский

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

Angewandte Chemie International Edition, Journal Year: 2023, Volume and Issue: 62(30)

Published: May 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.

Language: Английский

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A rational design of functional porous frameworks for electrocatalytic CO₂reduction reaction

Chemical Society Reviews, Journal Year: 2023, Volume and Issue: 52(4), P. 1382 - 1427

Published: Jan. 1, 2023

Rational design of functional porous frameworks for electrocatalytic CO 2 reduction reaction.

Language: Английский

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Tuning the Coordination Environment of Carbon‐Based Single‐Atom Catalysts via Doping with Multiple Heteroatoms and Their Applications in Electrocatalysis

Advanced Materials, Journal Year: 2023, Volume and Issue: 35(38)

Published: Feb. 13, 2023

Abstract Carbon‐based single‐atom catalysts (SACs) are considered to be a perfect platform for studying the structure–activity relationship of different reactions due adjustability their coordination environment. Multi‐heteroatom doping has been demonstrated as an effective strategy tuning environment carbon‐based SACs and enhancing catalytic performance in electrochemical reactions. Herein, recently developed strategies multi‐heteroatom doping, focusing on regulation active sites by heteroatoms shells, summarized. In addition, correlation between activity investigated through representative experiments theoretical calculations various Finally, concerning certain shortcomings current multi‐heteroatoms, some suggestions put forward promote development field electrocatalysis.

Language: Английский

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Decorating Single‐Atomic Mn Sites with FeMn Clusters to Boost Oxygen Reduction Reaction

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

Published: Nov. 19, 2022

The regulation of electron distribution single-atomic metal sites by atomic clusters is an effective strategy to boost their intrinsic activity oxygen reduction reaction (ORR). Herein we report the construction Mn decorated with innovative combination post-adsorption and secondary pyrolysis. X-ray absorption spectroscopy confirms formation via Mn-N4 coordination bonding FeMn (FeMnac /Mn-N4 C), which has been demonstrated theoretically be conducive adsorption molecular O2 break O-O bond during ORR process. Benefiting from structural features above, FeMnac C catalyst exhibits excellent half-wave potential 0.79 V in 0.5 M H2 SO4 0.90 0.1 KOH as well preeminent Zn-air battery performance. Such synthetic may open up a route construct highly active catalysts tunable structures for diverse applications.

Language: Английский

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Electrocatalytic Synthesis of Essential Amino Acids from Nitric Oxide Using Atomically Dispersed Fe on N‐doped Carbon

Angewandte Chemie International Edition, Journal Year: 2023, Volume and Issue: 62(26)

Published: April 19, 2023

How to transfer industrial exhaust gases of nitrogen oxides into high-values product is significantly important and challenging. Herein, we demonstrate an innovative method for artificial synthesis essential α-amino acids from nitric oxide (NO) by reacting with α-keto through electrocatalytic process atomically dispersed Fe supported on N-doped carbon matrix (AD-Fe/NC) as the catalyst. A yield valine 32.1 μmol mgcat-1 delivered at -0.6 V vs. reversible hydrogen electrode, corresponding a selectivity 11.3 %. In situ X-ray absorption fine structure synchrotron radiation infrared spectroscopy analyses show that NO source converted hydroxylamine promptly nucleophilic attacked electrophilic center acid form oxime subsequent reductive hydrogenation occurred way amino acid. Over 6 kinds have been successfully synthesized gaseous can be also replaced liquid (NO3- ). Our findings not only provide creative converting high-valued products, which epoch-making significance towards acids, but benefit in deploying near-zero-emission technologies global environmental economic development.

Language: Английский

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