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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Single-Atom Catalysts Based on the Metal–Oxide Interaction

Chemical Reviews, Journal Year: 2020, Volume and Issue: 120(21), P. 11986 - 12043

Published: Oct. 28, 2020

Metal atoms dispersed on the oxide supports constitute a large category of single-atom catalysts. In this review, supported catalysts are discussed about their synthetic procedures, characterizations, and reaction mechanism in thermocatalysis, such as water-gas shift reaction, selective oxidation/hydrogenation, coupling reactions. Some typical materials, including ferric oxide, cerium titanium dioxide, aluminum so on, intentionally mentioned for unique roles anchoring metal taking part catalytic The interactions between summarized to give picture how stabilize atomic centers, rationally tune geometric structures electronic states single atoms. Furthermore, several directions fabricating with improved performance proposed basis state-of-the-art understanding metal-oxide interactions.

Language: Английский

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Single-atom catalysis in advanced oxidation processes for environmental remediation

Chemical Society Reviews, Journal Year: 2021, Volume and Issue: 50(8), P. 5281 - 5322

Published: Jan. 1, 2021

This review presents the recent advances in synthetic strategies, characterisation, and computations of carbon-based single-atom catalysts, as well their innovative applications mechanisms advanced oxidation technologies.

Language: Английский

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Single-atom catalysts for photocatalytic energy conversion

Joule, Journal Year: 2022, Volume and Issue: 6(1), P. 92 - 133

Published: Jan. 1, 2022

Artificial photocatalytic energy conversion represents a highly intriguing strategy for solving the crisis and environmental problems by directly harvesting solar energy. The development of efficient photocatalysts is central task pushing real-world application reactions. Due to maximum atomic utilization efficiency distinct advantages outstanding catalytic activity, single-atom catalysts (SACs) have emerged as promising candidates photocatalysts. In current review, recent progresses challenges on SACs systems are presented. Fundamental principles focusing charge separation/transfer molecular adsorption/activation photocatalysis systemically explored. We outline how isolated reactive sites facilitate photogenerated electron–hole transfer promote construction photoactivation cycles. widespread adoption in diverse reactions also comprehensively introduced. By presenting these advances addressing some future with potential solutions related integral over SACs, we expect shed light forthcoming research conversion.

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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Identifying and tailoring C–N coupling site for efficient urea synthesis over diatomic Fe–Ni catalyst

Nature Communications, Journal Year: 2022, Volume and Issue: 13(1)

Published: Sept. 10, 2022

Electrocatalytic urea synthesis emerged as the promising alternative of Haber-Bosch process and industrial synthetic protocol. Here, we report that a diatomic catalyst with bonded Fe-Ni pairs can significantly improve efficiency electrochemical synthesis. Compared isolated single-atom catalysts, act efficient sites for coordinated adsorption activation multiple reactants, enhancing crucial C-N coupling thermodynamically kinetically. The performance up to an order magnitude higher than those electrocatalysts, high yield rate 20.2 mmol h-1 g-1 corresponding Faradaic 17.8% has been successfully achieved. A total about 100% formation value-added urea, CO, NH3 was realized. This work presents insight into synergistic catalysis towards sustainable via identifying tailoring atomic site configurations.

Language: Английский

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Altering Ligand Fields in Single-Atom Sites through Second-Shell Anion Modulation Boosts the Oxygen Reduction Reaction

Journal of the American Chemical Society, Journal Year: 2022, Volume and Issue: 144(5), P. 2197 - 2207

Published: Jan. 28, 2022

Single-atom catalysts based on metal-N4 moieties and anchored carbon supports (defined as M-N-C) are promising for oxygen reduction reaction (ORR). Among those, M-N-C with 4d 5d transition metal (TM4d,5d) centers much more durable not susceptible to the undesirable Fenton reaction, especially compared 3d ones. However, ORR activity of these TM4d,5d-N-C is still far from satisfactory; thus far, there few discussions about how accurately tune ligand fields single-atom TM4d,5d sites in order improve their catalytic properties. Herein, we leverage Ru-N-C a model system report an S-anion coordination strategy modulate catalyst's structure performance. The S anions identified bond N atoms second shell Ru centers, which allows us manipulate electronic configuration central sites. S-anion-coordinated catalyst delivers only but also outstanding long-term durability, superior those commercial Pt/C most near-term catalysts. DFT calculations reveal that high attributed lower adsorption energy intermediates at Metal-air batteries using this cathode side exhibit fast kinetics excellent stability.

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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Design of Local Atomic Environments in Single‐Atom Electrocatalysts for Renewable Energy Conversions

Advanced Materials, Journal Year: 2020, Volume and Issue: 33(5)

Published: Dec. 6, 2020

Abstract Single‐atom electrocatalysts (SAECs) have recently attracted tremendous research interest due to their often remarkable catalytic responses, unmatched by conventional catalysts. The electrocatalytic performance of SAECs is closely related the specific metal species and local atomic environments, including coordination number, determined structure sites, chemical identity nearest second neighboring atoms. wide range distinct bonding configurations a single‐metal atom with its surrounding host atoms creates virtually limitless opportunities for rational design synthesis tunable environment high‐performance electrocatalysis. In this review, authors first identify fundamental hurdles in electrochemical conversions highlight relevance SAECs. They then critically examine role structures, encompassing spheres isolated atoms, on single‐atom dopants activation also discussed. Insights into correlation between structures response are analyzed Finally, summarize major challenges be addressed field provide some perspectives construction superior conversions.

Language: Английский

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Architectural Design for Enhanced C₂ Product Selectivity in Electrochemical CO₂ Reduction Using Cu-Based Catalysts: A Review

ACS Nano, Journal Year: 2021, Volume and Issue: 15(5), P. 7975 - 8000

Published: May 6, 2021

Electrochemical CO2 reduction to value-added chemicals and fuels is a promising approach mitigate the greenhouse effect arising from anthropogenic emission energy shortage caused by depletion of nonrenewable fossil fuels. The generation multicarbon (C2+) products, especially hydrocarbons oxygenates, great interest for industrial applications. To date, Cu only metal known catalyze C–C coupling in electrochemical reaction (eCO2RR) with appreciable efficiency kinetic viability produce wide range C2 products aqueous solutions. Nonetheless, poor product selectivity associated main technical problem application eCO2RR technology on global scale. Based extensive research efforts, delicate rational design electrocatalyst architecture using principles nanotechnology likely significantly affect adsorption energetics some key intermediates hence inherent pathways. In this review, we summarize recent progress that has been achieved tailoring efficient conversion target products. By considering experimental computational results, further analyze underlying correlations between catalyst its toward Finally, major challenges are outlined, directions future development suggested.

Language: Английский

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