Tuning the Coordination Structure of CuNC Single Atom Catalysts for Simultaneous Electrochemical Reduction of CO₂ and NO₃^– to Urea

Advanced Energy Materials, Journal Year: 2022, Volume and Issue: 12(32)

Published: July 8, 2022

Abstract Closing both the carbon and nitrogen loops is a critical venture to support establishment of circular, net‐zero economy. Although single atom catalysts (SACs) have gained interest for electrochemical reduction reactions dioxide (CO 2 RR) nitrate (NO 3 RR), structure–activity relationship Cu SAC coordination these remains unclear should be explored such that fundamental understanding developed. To this end, role structure investigated in dictating activity selectivity CO RR NO RR. In agreement with density functional theory calculations, it revealed Cu‐N 4 sites exhibit higher intrinsic toward RR, whilst 4− x ‐C are active Leveraging findings, coupled formation urea on SACs, revealing importance *COOH binding as parameter determining catalytic production. best authors’ knowledge, first report employing SACs synthesis from which achieves Faradaic efficiency 28% production current − 27 mA cm –2 at 0.9 V versus reversible hydrogen electrode.

Language: Английский

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Engineering the Local Atomic Environments of Indium Single‐Atom Catalysts for Efficient Electrochemical Production of Hydrogen Peroxide

Angewandte Chemie International Edition, Journal Year: 2022, Volume and Issue: 61(12)

Published: Jan. 19, 2022

The in-depth understanding of local atomic environment-property relationships p-block metal single-atom catalysts toward the 2 e- oxygen reduction reaction (ORR) has rarely been reported. Here, guided by first-principles calculations, we develop a heteroatom-modified In-based metal-organic framework-assisted approach to accurately synthesize an optimal catalyst, in which single In atoms are anchored combined N,S-dual first coordination and B second supported hollow carbon rods (In SAs/NSBC). SAs/NSBC catalyst exhibits high H2 O2 selectivity above 95 % wide range pH. Furthermore, SAs/NSBC-modified natural air diffusion electrode unprecedented production rate 6.49 mol peroxide gcatalyst-1 h-1 0.1 M KOH electrolyte 6.71 PBS electrolyte. This strategy enables design next-generation high-performance materials, provides practical guidance for electrosynthesis.

Language: Английский

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Long‐Range Interactions in Diatomic Catalysts Boosting Electrocatalysis

Angewandte Chemie International Edition, Journal Year: 2022, Volume and Issue: 61(52)

Published: Oct. 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.

Language: Английский

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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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Lattice‐Matching Formed Mesoporous Transition Metal Oxide Heterostructures Advance Water Splitting by Active Fe–O–Cu Bridges

Advanced Energy Materials, Journal Year: 2022, Volume and Issue: 12(19)

Published: April 8, 2022

Abstract Developing efficient bifunctional electrocatalysts toward oxygen/hydrogen evolution reactions is crucial for electrochemical water splitting hydrogen production. The high‐performance depend on the catalytically active and highly accessible reaction sites their structural robustness, while rational design of such with desired features avoiding tedious manufacture still challenging. Here, a facile method reported to synthesize mesoporous heterostructured transition metal oxides strongly anchored nickel skeleton (MH‐TMO) containing identified Fe–Cu oxide interfaces high intrinsic activity, easy accessibility intermediates, long‐term stability alkaline reactions. MH‐TMO electrocatalytically Fe–O–Cu bridge has an optimal oxygen binding energy facilitate adsorption/desorption intermediates molecules. Associated mass transport through nanoporous structure, exhibits impressive catalysis, extremely low overpotential around 0.22 V at 10 mA cm −2 Tafel slope (44.5 mV dec −1 ) in 1.0 M KOH, realizing current density 100 as 0.26 V. As result, electrolyzer assembled by catalysts operates outstanding overall water‐splitting output (1.49 V@10 ), outperforming one noble‐metal‐based catalysts.

Language: Английский

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A Site Distance Effect Induced by Reactant Molecule Matchup in Single‐Atom Catalysts for Fenton‐Like Reactions

Angewandte Chemie International Edition, Journal Year: 2022, Volume and Issue: 61(33)

Published: June 20, 2022

Abstract Understanding the site interaction nature of single‐atom catalysts (SACs), especially densely populated SACs, is vital for their application to various catalytic reactions. Herein, we report a distance effect, which emphasizes how well adjacent copper atoms (denoted as d Cu1−Cu1 ) matches with reactant peroxydisulfate (PDS) molecular size determine Fenton‐like reaction reactivity on carbon‐supported SACs. The optimized in range 5–6 Å, PDS, endows catalyst nearly two times higher turnover frequency than that beyond this range, accordingly achieving record‐breaking kinetics oxidation emerging organic contaminants. Further studies suggest effect originates from alteration PDS adsorption dual‐site structure Cu 1 −Cu sites when falls within significantly enhancing interfacial charge transfer and consequently resulting most efficient activation so far.

Language: Английский

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Single‐atom catalysis for carbon neutrality

Carbon Energy, Journal Year: 2022, Volume and Issue: 4(6), P. 1021 - 1079

Published: July 14, 2022

Abstract Currently, more than 86% of global energy consumption is still mainly dependent on traditional fossil fuels, which causes resource scarcity and even emission high amounts carbon dioxide (CO 2 ), resulting in a severe “Greenhouse effect.” Considering this situation, the concept “carbon neutrality” has been put forward by 125 countries one after another. To achieve goals neutrality,” two main strategies to reduce CO emissions develop sustainable clean can be adopted. Notably, these are crucial for synthesis advanced single‐atom catalysts (SACs) energy‐related applications. In review, we highlight unique SACs conversion into high‐efficiency energy, example, through photocatalytic, electrocatalytic, thermal catalytic hydrogenation technologies, convert hydrocarbon fuels (CO, CH 4 , HCOOH, 3 OH, multicarbon [C 2+ ] products). addition, introduce technologies devices replace polluting such as photocatalytic electrocatalytic water splitting produce hydrogen oxygen reduction reaction (ORR) fuel cells. Impressively, several representative examples (including d ‐, ds p f ‐blocks) conversion, H ORR discussed describe methods, characterization, corresponding activity. Finally, review concludes with description challenges outlooks future applications contributing toward neutrality.

Language: 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, Journal Year: 2023, Volume and Issue: 62(15)

Published: Feb. 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.

Language: 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, Journal Year: 2022, Volume and Issue: 144(42), P. 19619 - 19626

Published: Oct. 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.

Language: Английский

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Dual‐Atom Support Boosts Nickel‐Catalyzed Urea Electrooxidation

Angewandte Chemie International Edition, Journal Year: 2023, Volume and Issue: 62(22)

Published: March 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.

Language: Английский

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