Tackling the Activity and Selectivity Challenges of Electrocatalysts toward the Nitrogen Reduction Reaction via Atomically Dispersed Biatom Catalysts

Journal of the American Chemical Society, Journal Year: 2020, Volume and Issue: 142(12), P. 5709 - 5721

Published: Feb. 18, 2020

Developing efficient catalysts for nitrogen fixation is becoming increasingly important but still challenging due to the lack of robust design criteria tackling activity and selectivity problems, especially electrochemical reduction reaction (NRR). Herein, by means large-scale density functional theory (DFT) computations, we reported a descriptor-based principle explore large composition space two-dimensional (2D) biatom (BACs), namely, metal dimers supported on 2D expanded phthalocyanine (M2-Pc or MM'-Pc), toward NRR at acid conditions. We sampled both homonuclear (M2-Pc) heteronuclear (MM'-Pc) BACs constructed map using N2H* adsorption energy as descriptor, which reduces number promising catalyst candidates from over 900 less than 100. This strategy allowed us readily identify 3 28 BACs, could break metal-based benchmark NRR. Particularly, free difference H* screened out five systems, including Ti2-Pc, V2-Pc, TiV-Pc, VCr-Pc, VTa-Pc, exhibit strong capability suppressing competitive hydrogen evolution (HER) with favorable limiting potential -0.75, -0.39, -0.74, -0.85, -0.47 V, respectively. work not only broadens possibility discovering more N2 also provides feasible rational electrocatalysts helps pave way fast screening other reactions.

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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Theoretical insights into single-atom catalysts

Chemical Society Reviews, Journal Year: 2020, Volume and Issue: 49(22), P. 8156 - 8178

Published: Jan. 1, 2020

Single-atom catalysts (SACs) with atomically dispersed metals have emerged as a new class of heterogeneous and attracted considerable interest because they offer 100% metal atom utilization show excellent catalytic behavior compared traditionally supported nano-particles. However, it is challenging to explore the active sites mechanisms SACs through common characterization methods due isolated single atoms. Therefore, employing theoretical calculations determine nature SACs' reaction particularly meaningful. This paper describes by summarizing diverse applications properties SACs, which starts from computational simulation on couple important SACs. Then distinctive fundamental are discussed. At last, challenges future perspectives for outlined.

Language: Английский

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Recent Progress of Electrochemical Production of Hydrogen Peroxide by Two‐Electron Oxygen Reduction Reaction

Advanced Science, Journal Year: 2021, Volume and Issue: 8(15)

Published: May 27, 2021

Shifting electrochemical oxygen reduction reaction (ORR) via two-electron pathway becomes increasingly crucial as an alternative/green method for hydrogen peroxide (H2 O2 ) generation. Here, the development of 2e- ORR catalysts in recent years is reviewed, aspects mechanism exploration, types high-performance catalysts, factors to influence catalytic performance, and potential applications ORR. Based on previous theoretical experimental studies, underlying firstly unveiled, aspect pathway, thermodynamic free energy diagram, limiting potential, volcano plots. Then, various efficient producing H2 are summarized. Additionally, active sites catalysts' such electronic structure, carbon defect, functional groups (O, N, B, S, F etc.), synergistic effect, others (pH, pore steric hindrance etc.) discussed. The electrogeneration also has wastewater treatment, disinfection, organics degradation, storage. Finally, future directions prospects electrochemically examined. These insights may help develop highly active/selective shape application this method.

Language: Английский

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High-Throughput Screening of Synergistic Transition Metal Dual-Atom Catalysts for Efficient Nitrogen Fixation

Nano Letters, Journal Year: 2021, Volume and Issue: 21(4), P. 1871 - 1878

Published: Feb. 15, 2021

Great enthusiasm in single-atom catalysts (SACs) for the nitrogen reduction reaction (NRR) has been aroused by discovery of metal–Nx as a promising catalytic center. However, poor activity and low selectivity available SACs are far away from industrial requirement. Through first-principles high-throughput screening, we find that Fe–Fe distributed on graphite carbon nitride (Fe2/g-CN) can manipulate binding strength target species (compromises ability to adsorb N2H NH2), therefore achieving best NRR performance among 23 transition metal (TM) centers. Our results show Fe2/g-CN achieves high theoretical Faradaic efficiency 100% and, impressively, lowest limiting potential −0.13 V. Particularly, multiple-level descriptors shed light origin activity, fast prescreening various candidates. predictions not only accelerate ammonia synthesis but also contribute further elucidate structure–performance correlations.

Language: Английский

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“More is Different:” Synergistic Effect and Structural Engineering in Double‐Atom Catalysts

Advanced Functional Materials, Journal Year: 2020, Volume and Issue: 31(3)

Published: Nov. 16, 2020

Abstract Double‐atom catalysts (DACs) have emerged as a novel frontier in heterogeneous catalysis because the synergistic effect between adjacent active sites can promote their catalytic activity while maintaining high atomic utilization efficiency, good selectivity, and stability originating from atomically dispersed nature. In this review, recent progress both experimental theoretical research on DACs for various reactions is focused. Specifically, central tasks design of DACs—manipulating engineering electronic structures catalysts—are systematically reviewed, along with prevailing experimental, characterization, computational modeling approaches. Furthermore, practical applications water splitting, oxygen reduction reaction, nitrogen carbon dioxide reaction are addressed. Finally, future challenges summarized an outlook further investigations toward high‐performance energy environmental provided.

Language: Английский

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Recent Advances in Electrochemical Oxygen Reduction to H₂O₂: Catalyst and Cell Design

ACS Energy Letters, Journal Year: 2020, Volume and Issue: 5(6), P. 1881 - 1892

Published: May 8, 2020

Electrochemical production of H2O2 from O2 is a promising alternative to the energy-intensive anthraquinone process that currently used as an industry standard. Although most research on oxygen reduction reaction (ORR) has focused 4-electron pathway water relevant fuel cells, 2-electron ORR produce also significant commercial interest. The first half this Perspective deals with progress made in developing noble metal, carbon-based, and single-atom electrocatalysts highlights design strategies employed obtain high selectivity toward H2O2. second addresses challenges large-scale how results obtained using rotating ring disk electrode (RRDE) can be translated into commercially viable flow cells. This focuses catalysts cells will enable industrial-scale electrochemical production.

Language: Английский

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Catalyst Design for Electrochemical Oxygen Reduction toward Hydrogen Peroxide

Advanced Functional Materials, Journal Year: 2020, Volume and Issue: 30(35)

Published: June 18, 2020

Abstract Precise electrochemical synthesis under ambient conditions has provided emerging opportunities for renewable energy utilization. Among many promising systems, the production of hydrogen peroxide (H 2 O ) from cathodic oxygen reduction reaction (ORR) attracted considerable interest in past decades due to increasing market demands and vital role ORR electrocatalysis field. This work describes recent advances materials H 2e - ORR. By using Pt as a stereotype, tuning knobs are overviewed, including intrinsic binding strength oxygenated species, intermediate diffusion path isolation Pt–Pt ensembles that enable pathway 4e total reduction. knowledge is successfully applied other transition metal systems leads discovery more efficient alloy catalysts with balanced improvement on both activity selectivity. In addition, mesostructure engineering heteroatoms doping strategies carbon‐based materials, which significantly boost efficiency compared intact carbon sites, also reviewed. Finally, future directions challenges transferring developed lab scale tests pilot plant operations briefly outlooked.

Language: Английский

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Synthesis Strategies, Catalytic Applications, and Performance Regulation of Single‐Atom Catalysts

Advanced Functional Materials, Journal Year: 2021, Volume and Issue: 31(12)

Published: Jan. 4, 2021

Abstract The recent dramatic increase in research on isolated metal atoms has received extensive scientific interest the new frontier of single‐atom catalysis. As newly advanced materials catalysis, catalysts (SACs) have enormous from perspectives both and industrial applications due to their remarkable activity. In addition, other catalytic properties single atoms, including stability selectivity, can be further improved by tuning electronic/geometric structures modulating metal–support interactions. SACs usually consist dispersed appropriate support materials, which are employed anchor, confine, and/or coordinate with atoms. Therefore, nature sites allows acquiring a maximum atom utilization approaching 100%, is significance, particularly for development noble‐metal‐based catalysts. order systematically understand structure–property relationships underlying mechanisms relationship SACs, representative efforts synthesis strategies, applications, performance regulation discussed here. Typical catalysis processes corresponding electrochemistry, photochemistry, organic synthesis, biomedicine also summarized. Finally, challenges prospects highlighted.

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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