Synergistic Effect of Oxygen Vacancy and High Porosity of Nano MIL‐125(Ti) for Enhanced Photocatalytic Nitrogen Fixation

Angewandte Chemie International Edition, Journal Year: 2023, Volume and Issue: 63(3)

Published: Dec. 5, 2023

This work reports that a low-temperature thermal calcination strategy was adopted to modulate the electronic structure and attain an abundance of surface-active sites while maintaining crystal morphology. All experiments demonstrate new photocatalyst nano MIL-125(Ti)-250 obtained by has abundant Ti

Language: Английский

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Optimizing Electrocatalytic Nitrogen Reduction via Interfacial Electric Field Modulation: Elevating d‐Band Center in WS₂‐WO₃ for Enhanced Intermediate Adsorption

Angewandte Chemie International Edition, Journal Year: 2023, Volume and Issue: 62(29)

Published: May 25, 2023

Electrocatalytic nitrogen reduction reaction (ENRR) has emerged as a promising approach to synthesizing green ammonia under ambient conditions. Tungsten (W) is one of the most effective ENRR catalysts. In this reaction, protonation intermediates rate-determining step (RDS). Enhancing adsorption crucial increase intermediates, which can lead improved catalytic performance. Herein, we constructed strong interfacial electric field in WS2 -WO3 elevate d-band center W, thereby strengthening intermediates. Experimental results demonstrated that led significantly Specifically, exhibited high NH3 yield 62.38 μg h-1 mgcat-1 and promoted faraday efficiency (FE) 24.24 %. Furthermore, situ characterizations theoretical calculations showed upshifted W towards Fermi level, leading enhanced -NH2 -NH on catalyst surface. This resulted rate RDS. Overall, our study offers new insights into relationship between provides strategy enhance during process.

Language: Английский

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Metalation of metal–organic frameworks: fundamentals and applications

Chemical Society Reviews, Journal Year: 2024, Volume and Issue: 53(11), P. 5626 - 5676

Published: Jan. 1, 2024

Metalation of metal-organic frameworks (MOFs) has been developed as a prominent strategy for materials functionalization pore chemistry modulation and property optimization. By introducing exotic metal ions/complexes/nanoparticles onto/into the parent framework, many metallized MOFs have exhibited significantly improved performance in wide range applications. In this review, we focus on research progress metalation during last five years, spanning design principles, synthetic strategies, potential Based crystal engineering minor change MOF composition through would lead to leveraged variation properties. This review starts from general strategies established incorporation species within MOFs, followed by principles graft desired functionality while maintaining porosity frameworks. Facile contributed great number bespoke with excellent performance, summarize their applications gas adsorption separation, heterogeneous catalysis, detection sensing, energy storage conversion. The underlying mechanisms are also investigated state-of-the-art techniques analyzed gaining insight into structure-property relationships, which turn facilitate further development principles. Finally, current challenges opportunities discussed, promising future directions customizing next-generation advanced outlined well.

Language: Английский

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Regulating Intramolecular Electron Transfer of Nickel‐Based Coordinations through Ligand Engineering for Aqueous Batteries

Advanced Materials, Journal Year: 2023, Volume and Issue: 35(48)

Published: Sept. 25, 2023

The integration of electronic effects into complexes for the construction novel materials has not yet attracted significant attention in field energy storage. In current study, eight one-dimensional (1D) nickel-based salicylic acid (Ni-XSAs, X = pH, pMe, pMeO, mMe, pBr, pCl, pF, and pCF3 ), are prepared by ligand engineering. coordination environments Ni-XSAs explored using X-ray absorption fine structure spectroscopy. charge transfer is modulated according to difference electron-donating ability substituents, combination with frontier orbital theory. Furthermore, density functional theory used investigate effect substituent position on properties complexes. Ni-mMeSA exhibits better electrical conductivity than Ni-pMeSA. electrochemical performance as an aqueous battery cathode remarkably improved a maximum 0.30 mWh cm-2 (125 Wh kg-1 ) peak power 33.72 mW (14.03 kW ). This study provides ideas application new chemistry science.

Language: Английский

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Synergistic Effect of Oxygen Vacancy and High Porosity of Nano MIL‐125(Ti) for Enhanced Photocatalytic Nitrogen Fixation

Angewandte Chemie, Journal Year: 2023, Volume and Issue: 136(3)

Published: Dec. 5, 2023

Abstract This work reports that a low‐temperature thermal calcination strategy was adopted to modulate the electronic structure and attain an abundance of surface‐active sites while maintaining crystal morphology. All experiments demonstrate new photocatalyst nano MIL‐125(Ti)‐250 obtained by has abundant Ti 3+ induced oxygen vacancies high specific surface area. facilitates adsorption activation N 2 molecules on active in photocatalytic nitrogen fixation. The NH 3 yield over is enhanced 156.9 μmol g −1 h , twice higher than parent MIL‐125(Ti) (76.2 ). Combined with density function theory (DFT), it shows pattern tends be from “end‐on” “side‐on” mode, which thermodynamically favourable. Moreover, electrochemical tests atomic ratio /Ti 4+ can enhance carrier separation, also promotes efficiency may offer insights into design innovative photocatalysts for various chemical reduction reactions.

Language: Английский

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Recent Advances in Electrocatalytic Hydrogenation Reactions on Copper‐Based Catalysts

Advanced Materials, Journal Year: 2023, Volume and Issue: 36(14)

Published: Sept. 27, 2023

Hydrogenation reactions play a critical role in the synthesis of value-added products within chemical industry. Electrocatalytic hydrogenation (ECH) using water as hydrogen source has emerged an alternative to conventional thermocatalytic processes for sustainable and decentralized under mild conditions. Among various ECH catalysts, copper-based (Cu-based) nanomaterials are promising candidates due their earth-abundance, unique electronic structure, versatility, high activity/selectivity. Herein, recent advances application Cu-based catalysts upgrading valuable chemicals systematically analyzed. The properties initially introduced, followed by design strategies enhance activity selectivity. Then, typical on presented detail, including carbon dioxide reduction multicarbon generation, alkyne-to-alkene conversion, selective aldehyde ammonia production from nitrogen-containing substances, amine organic nitrogen compounds. In these catalyst composition nanostructures toward different is focused. co-hydrogenation two substrates (e.g., CO

Language: Английский

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Biomimetic Design of a Dynamic M–O–V Pyramid Electron Bridge for Enhanced Nitrogen Electroreduction

Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: 146(11), P. 7752 - 7762

Published: March 6, 2024

Electrochemical nitrogen reduction reaction (eNRR) offers a sustainable route for ammonia synthesis; however, current electrocatalysts are limited in achieving optimal performance within narrow potential windows. Herein, inspired by the heliotropism of sunflowers, we present biomimetic design Ru-VOH electrocatalyst, featuring dynamic Ru–O–V pyramid electron bridge eNRR wide range. In situ spectroscopy and theoretical investigations unravel fact that electrons donated from Ru to V at lower overpotentials retrieved higher overpotentials, maintaining delicate balance between N2 activation proton hydrogenation. Moreover, adsorption were found be enhanced moiety. The catalyst showcases an outstanding Faradaic efficiency 51.48% −0.2 (vs RHE) with NH3 yield rate exceeding 115 μg h–1 mg–1 across range −0.4 RHE), along impressive durability over 100 cycles. This M–O–V is also applicable other metals (M = Pt, Rh, Pd).

Language: Английский

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Modulating electronic structures of MOF through orbital rehybridization by Cu doping promotes photocatalytic reduction of nitrate to produce ammonia

Nano Energy, Journal Year: 2024, Volume and Issue: 124, P. 109499 - 109499

Published: March 16, 2024

Language: Английский

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Recent Progress on Computation‐Guided Catalyst Design for Highly Efficient Nitrogen Reduction Reaction

Advanced Functional Materials, Journal Year: 2024, Volume and Issue: 34(34)

Published: April 5, 2024

Abstract Electrochemical nitrogen reduction reaction (NRR) for ammonia synthesis has attracted great interest in recent years, which presents a carbon‐free alternative to the energy‐intensive Haber–Bosch process. Besides, NRR also provides promising coverage route of renewable energy since NH 3 is considered second generation hydrogen while possessing established technologies liquefaction, storage, and transport. However, there are long‐term challenges catalyst design due its low intrinsic activity unsatisfied selectivity. Fortunately, by conducting extensive explorations this field, much progress achieved boosting performance. Herein, from view atomic/electronic level, three promotion effects summarized (i.e., electron effect, geometry ligand effect), tackle Representative studies with taking fully advantages reviewed, realized remarkable Finally, future research directions prospects discussed. It highly expected that review will enable advancement catalysts promote further development electrochemical NRR.

Language: Английский

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A Coherent Pd–Pd₁₆B₃ Core–Shell Electrocatalyst for Controlled Hydrogenation in Nitrogen Reduction Reaction

Advanced Functional Materials, Journal Year: 2024, Volume and Issue: 34(34)

Published: March 7, 2024

Abstract The manipulation of surface catalytic sites has rarely been explored for metal borides, and the subsurface effects on electrocatalytic activity nitrogen reduction reaction (NRR) remain unknown. Herein, this work develops a core–shell nanoparticle catalyst with Pd core that ensures high electron transfer rates an 16 B 3 atomical shell possess tunable active regulating NRR. atomic structural evolution from to is investigated by precisely controlling atom diffusion, molecular rearrangement, d – sp orbital hybridization. Pd/Pd nanocrystals exhibit exceptional NRR performance NH Faradaic efficiency 30.8%, which superior those pristine (1.2%) B‐doped (4.8%) under identical conditions, yield rate 0.81 µmol h −1 cm −2 . This discovers could promote selectivity separating hydrogen proceeded hole bridge sites, provide excellent conductivity through regulated interactions. Consequently, controlled chemical ordering palladium boride surfaces provides insight into synthesis advanced electrocatalysts.

Language: Английский

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