Tailoring Acidic Oxygen Reduction Selectivity on Single-Atom Catalysts via Modification of First and Second Coordination Spheres

Journal of the American Chemical Society, Journal Year: 2021, Volume and Issue: 143(20), P. 7819 - 7827

Published: May 13, 2021

Product selectivity in multielectron electrocatalytic reactions is crucial to energy conversion efficiency and chemical production. However, a present practical drawback the limited understanding of actual catalytic active sites. Here, using as prototype single-atom catalysts (SACs) acidic oxygen reduction reaction (ORR), we report structure–property relationship show for first time that molecular-level local structure, including second coordination spheres (CSs), rather than individual atoms, synergistically determines response. ORR on Co-SACs can be tailored from four-electron two-electron pathway by modifying (N or/and O coordination) (C–O–C groups) CSs. Using combined theoretical predictions experiments, X-ray absorption fine structure analyses situ infrared spectroscopy, confirm unique change originates structure-dependent shift sites center Co atom O-adjacent C atom. We this optimizes electronic *OOH adsorption behavior give "best" activity >95% H2O2 electrosynthesis.

Language: Английский

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Electronic metal–support interaction modulates single-atom platinum catalysis for hydrogen evolution reaction

Nature Communications, Journal Year: 2021, Volume and Issue: 12(1)

Published: May 21, 2021

Tuning metal-support interaction has been considered as an effective approach to modulate the electronic structure and catalytic activity of supported metal catalysts. At atomic level, understanding structure-activity relationship still remains obscure in heterogeneous catalysis, such conversion water (alkaline) or hydronium ions (acid) hydrogen (hydrogen evolution reaction, HER). Here, we reveal that fine control over oxidation states single-atom Pt catalysts through significantly modulates activities either acidic alkaline HER. Combined with detailed spectroscopic electrochemical characterizations, is established by correlating acidic/alkaline HER average state Pt-H/Pt-OH interaction. This study sheds light on atomic-level mechanistic HER, further provides guidelines for rational design high-performance

Language: Английский

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Engineering Dual Single‐Atom Sites on 2D Ultrathin N‐doped Carbon Nanosheets Attaining Ultra‐Low‐Temperature Zinc‐Air Battery

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

Published: Jan. 7, 2022

Herein, a novel dual single-atom catalyst comprising adjacent Fe-N4 and Mn-N4 sites on 2D ultrathin N-doped carbon nanosheets with porous structure (FeMn-DSAC) was constructed as the cathode for flexible low-temperature Zn-air battery (ZAB). FeMn-DSAC exhibits remarkable bifunctional activities oxygen reduction reaction (ORR) evolution (OER). Control experiments density functional theory calculations reveal that catalytic activity arises from cooperative effect of Fe/Mn dual-sites aiding *OOH dissociation well nanosheet promoting active sits exposure mass transfer during process. The excellent enables ZAB to operate efficiently at ultra-low temperature -40 °C, delivering 30 mW cm-2 peak power retaining up 86 % specific capacity room counterpart.

Language: Английский

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Design concept for electrocatalysts

Nano Research, Journal Year: 2021, Volume and Issue: 15(3), P. 1730 - 1752

Published: Sept. 4, 2021

Language: Английский

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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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Metal–Organic Frameworks Derived Functional Materials for Electrochemical Energy Storage and Conversion: A Mini Review

Nano Letters, Journal Year: 2021, Volume and Issue: 21(4), P. 1555 - 1565

Published: Feb. 11, 2021

With many apparent advantages including high surface area, tunable pore sizes and topologies, diverse periodic organic–inorganic ingredients, metal–organic frameworks (MOFs) have been identified as versatile precursors or sacrificial templates for preparing functional materials advanced electrodes high-efficiency catalysts electrochemical energy storage conversion (EESC). In this Mini Review, we first briefly summarize the material design strategies to show rich possibilities of chemical compositions physical structures MOFs derivatives. We next highlight latest advances focusing on composition/structure/performance relationship discuss their practical applications in various EESC systems, such supercapacitors, rechargeable batteries, fuel cells, water electrolyzers, carbon dioxide/nitrogen reduction reactions. Finally, provide some our own insights into major challenges prospective solutions MOF-derived EESC, hoping shed light future development highly exciting field.

Language: Английский

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Theory-oriented screening and discovery of advanced energy transformation materials in electrocatalysis

Advanced Powder Materials, Journal Year: 2021, Volume and Issue: 1(1), P. 100013 - 100013

Published: Nov. 15, 2021

Various metal-based electrocatalysts from nanocrystals, to clusters and single-atoms, have been well-discovered towards high-efficient power devices electrocatalytic conversion. To accelerate energy transformation materials discovery, developing high-throughput DFT calculations machine-learning techniques is of great necessity. This review comprehensively outlines the latest progress theory-guided design advanced materials. Especially, we focus on study single atoms in various devices, such as fuel cell (oxygen reduction reaction, ORR; acid oxidation reaction; alcohol reaction), other reactions for energy-related conversion small molecules, H2O2 evolution (2e− ORR), water splitting (H2 reaction/O2 HER/OER), N2 reaction (NRR), CO2 (CO2RR). Firstly, electronic structure, interaction mechanism, activation path are discussed provide an overall blueprint electrocatalysis batteries mentioned above. Thereafter, experimental synthesis strategies, structural recognition, performance figured out. Finally, some viewpoints into current issues future concept provided.

Language: Английский

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Superiority of Dual‐Atom Catalysts in Electrocatalysis: One Step Further Than Single‐Atom Catalysts

Advanced Energy Materials, Journal Year: 2022, Volume and Issue: 12(9)

Published: Jan. 18, 2022

Abstract In recent years, dual‐atom catalysts (DACs) have attracted extensive attention, as an extension of single‐atom (SACs). Compared with SACs, DACs higher metal loading and more complex flexible active sites, thus achieving better catalytic performance providing opportunities for electrocatalysis. This review introduces the research progress in years on how to design new enhance Firstly, advantages increasing are introduced. Then, role changing adsorption condition reactant molecules atoms is discussed. Moreover, ways which can reduce reaction energy barrier key steps change path explored. Catalytic applications different electrocatalytic reactions, including carbon dioxide reduction reaction, oxygen evolution hydrogen nitrogen followed. Finally, a brief summary made challenges prospects

Language: Английский

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An Adjacent Atomic Platinum Site Enables Single‐Atom Iron with High Oxygen Reduction Reaction Performance

Angewandte Chemie International Edition, Journal Year: 2021, Volume and Issue: 60(35), P. 19262 - 19271

Published: June 22, 2021

Abstract The modulation effect has been widely investigated to tune the electronic state of single‐atomic M‐N‐C catalysts enhance activity oxygen reduction reaction (ORR). However, in‐depth study is rarely reported for isolated dual‐atomic metal sites. Now, catalytic activities Fe‐N 4 moiety can be enhanced by adjacent Pt‐N through effect, in which acts as modulator 3d orbitals active site and optimize ORR activity. Inspired this principle, we design synthesize electrocatalyst that comprises /Pt‐N moieties dispersed nitrogen‐doped carbon matrix (Fe‐N @NC) exhibits a half‐wave potential 0.93 V vs. RHE negligible degradation (ΔE 1/2 =8 mV) after 10000 cycles 0.1 M KOH. We also demonstrate not effective optimizing performances Co‐N Mn‐N systems.

Language: Английский

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Descriptors for the Evaluation of Electrocatalytic Reactions: d‐Band Theory and Beyond

Advanced Functional Materials, Journal Year: 2021, Volume and Issue: 32(4)

Published: Oct. 13, 2021

Abstract Closing the carbon‐, hydrogen‐, and nitrogen cycle with renewable electricity holds promises for mitigation of facing environment energy crisis, along continuing prosperity human society. Descriptors bridge gap between physicochemical factors electrocatalysts their boosted activity serve as guiding principles during rational design electrocatalysts. The optimal adsorption strength key intermediates is potentially accessed under tendentious guidelines proposed by indicators, such d‐band center, Δ G H , E O* coordination number (CN), bond length, etc. Here, in this review, a comprehensive summary recent advances achieved regarding descriptors that aims recycling C/H/N‐containing chemicals offered. review initiated providing necessity development efficient then physics behind center introduced. Then progress relating to guidance reviewed. Following that, an extended discussion experimental or theoretical characterization beyond it provided. Finally, perspectives challenges area are

Language: Английский

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