Sustainable Ammonia Electrosynthesis from Nitrate Wastewater Coupled to Electrocatalytic Upcycling of Polyethylene Terephthalate Plastic Waste

ACS Nano, Journal Year: 2023, Volume and Issue: 17(13), P. 12422 - 12432

Published: June 26, 2023

Integrating the nitrate reduction reaction (NO3RR) with polyethylene terephthalate (PET) hydrolysate oxidation to construct nitrate/PET coelectrolysis system holds a great promise of realizing simultaneous upcycling wastewater and PET plastic waste, which, however, is still an almost untouched research area. Herein, we develop ultralow content Ru-incorporated Co-based metal-organic frameworks as bifunctional precatalyst, which can be in situ reconstructed Ru-Co(OH)2 at cathode Ru-CoOOH anode under electrocatalytic environments, function real active catalysts for NO3RR oxidation, respectively. With two-electrode system, current density 50 mA cm-2 achieved cell voltage only 1.53 V, production ammonia formate lower energy consumption. This study provides concept construction systems waste.

Language: Английский

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Optimizing Intermediate Adsorption via Heteroatom Ensemble Effect over RuFe Bimetallic Alloy for Enhanced Nitrate Electroreduction to Ammonia

Advanced Energy Materials, Journal Year: 2023, Volume and Issue: 13(31)

Published: June 30, 2023

Abstract The electrochemical nitrate reduction reaction (NO 3 RR) is a promising approach for removal and NH synthesis at ambient conditions. As complex eight‐electron/nine‐proton transfer process, its performance relies heavily on the adsorption ability of intermediates catalyst surface, which determined by geometric electronic configurations active sites. In this work, heteroatom ensemble effect deliberately triggered over RuFe bimetallic alloy to optimize intermediate NO RR. A record‐high yield rate 118.8 mg h −1 high Faradaic efficiency 92.2% are achieved −1.4 V vs reversible hydrogen electrode, ranking top state‐of‐the‐art. Experimental computational results reveal that characteristics induced play crucial roles. Both Ru Fe display continuous state throughout Fermi level, suggesting electron density benefits whole result, facilitated − , efficient stabilization key intermediates, as well timely desorption simultaneously achieved, thus significantly promoting direct .

Language: Английский

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Crystal Phase Engineering of Ultrathin Alloy Nanostructures for Highly Efficient Electroreduction of Nitrate to Ammonia

Advanced Materials, Journal Year: 2024, Volume and Issue: 36(14)

Published: Jan. 26, 2024

Abstract Electrocatalytic nitrate reduction reaction (NO 3 RR) toward ammonia synthesis is recognized as a sustainable strategy to balance the global nitrogen cycle. However, it still remains great challenge achieve highly efficient production due complex proton‐coupled electron transfer process in NO RR. Here, controlled of RuMo alloy nanoflowers (NFs) with unconventional face‐centered cubic (fcc) phase and hexagonal close‐packed/fcc heterophase for RR reported. Significantly, fcc NFs demonstrate high Faradaic efficiency 95.2% large yield rate 32.7 mg h −1 cat at 0 −0.1 V (vs reversible hydrogen electrode), respectively. In situ characterizations theoretical calculations have unraveled that possess highest d‐band center superior electroactivity, which originates from strong Ru─Mo interactions intrinsic activity phase. The optimal electronic structures supply adsorption key intermediates suppression competitive evolution, further determines remarkable performance. successful demonstration high‐performance zinc‐nitrate batteries suggests their substantial application potential electrochemical energy systems.

Language: Английский

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Tandem Electrocatalytic Nitrate Reduction to Ammonia on MBenes

Angewandte Chemie, Journal Year: 2023, Volume and Issue: 135(13)

Published: Feb. 3, 2023

Abstract We demonstrate the great feasibility of MBenes as a new class tandem catalysts for electrocatalytic nitrate reduction to ammonia (NO 3 RR). As proof concept, FeB 2 is first employed model MBene catalyst NO RR, showing maximum NH ‐Faradaic efficiency 96.8 % with corresponding yield 25.5 mg h −1 cm −2 at −0.6 V vs. RHE. Mechanistic studies reveal that exceptional RR activity arises from catalysis mechanism, is, B sites activate − form intermediates, while Fe dissociate H O and increase *H supply on promote intermediate hydrogenation enhance ‐to‐NH conversion.

Language: Английский

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Atomically dispersed Cu coordinated Rh metallene arrays for simultaneously electrochemical aniline synthesis and biomass upgrading

Nature Communications, Journal Year: 2023, Volume and Issue: 14(1)

Published: Sept. 14, 2023

Organic electrocatalytic conversion is an essential pathway for the green of low-cost organic compounds to high-value chemicals, which urgently demands development efficient electrocatalysts. Here, we report a Cu single-atom dispersed Rh metallene arrays on foam cathodic nitrobenzene electroreduction reaction and anodic methanol oxidation reaction. In coupled system, Cusingle-atom-Rh requires only low voltages 1.18 V reach current densities 100 mA cm-2 generating aniline formate, with up ~100% conversion/ selectivity over ~90% formate Faraday efficiency, achieving synthesis chemicals. Density functional theory calculations reveal electron effect between host catalytic mechanism. The synergistic H*-spillover can improve process reduce energy barrier process, thus enhancing activity target product selectivity.

Language: Английский

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Tandem Electrocatalytic Reduction of Nitrite to Ammonia on Rhodium–Copper Single Atom Alloys

Advanced Functional Materials, Journal Year: 2024, Volume and Issue: 34(36)

Published: April 23, 2024

Abstract Electrocatalytic reduction of NO 2 − to NH 3 (NO RR) presents a fascinating approach for simultaneously migrating pollutants and producing valuable . In this study, single‐atom Rh‐alloyed copper (CuRh 1 ) is explored as highly active selective catalyst toward the RR. Combined theoretical calculations in situ FTIR/EPR spectroscopic experiments uncover synergistic effect Rh Cu promote RR energetics CuRh through tandem catalysis pathway, which activates preliminary adsorption hydrogenation → *NO *NOOH *NO), while generated on then transferred substrate promotes rate‐determining step *NHO synthesis. As result, equipped flow cell an unprecedented yield rate 2191.6 µmol h −1 cm −2 ‐Faradaic efficiency 98.9% at high current density 322.5 mA , well long‐term stability 100 electrolysis.

Language: Английский

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H* Species Regulation by Mn‐Co(OH)₂ for Efficient Nitrate Electro‐reduction in Neutral Solution

Angewandte Chemie International Edition, Journal Year: 2024, Volume and Issue: 63(11)

Published: Jan. 23, 2024

Abstract During the electrocatalytic NO 3 − reduction reaction (NO RR) under neutral condition, activation of H 2 O to generate H* and inhibition inter‐H* species binding, are critically important but remain challenging for suppressing non‐desirable hydrogen evolution (HER). Here, a Mn‐doped Co(OH) (named as Mn‐Co(OH) ) has been synthesized by in situ reconstruction electrolyte, which is able dissociate molecules inhibits binding between each other owing increased interatomic spacing Mn‐doping. The electrocatalyst offers faradaic efficiency (FE) high 98.9±1.7% at −0.6 V vs. reversible electrode (RHE) an energy (EE) 49.90±1.03% NH production RR, among highest recently reported state‐of‐the‐art catalysts electrolyte. Moreover, negligible degradation −200 mA cm −2 found least 500 h, longest catalytic durations ever reported. This work paves novel approach design synthesis efficient RR electrocatalysts.

Language: Английский

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Main-group indium single-atom catalysts for electrocatalytic NO reduction to NH₃

Journal of Materials Chemistry A, Journal Year: 2023, Volume and Issue: 11(13), P. 6814 - 6819

Published: Jan. 1, 2023

In single atoms confined in amorphous MoO 3 (In 1 /a-MoO ) are reported to be an efficient catalyst for NO electroreduction NH , attributed the ability of single-site inhibit hydrogen evolution and optimize NO-to-NH hydrogenation energetics.

Language: Английский

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Electrochemical NO₃^– Reduction Catalyzed by Atomically Precise Ag₃₀Pd₄ Bimetallic Nanocluster: Synergistic Catalysis or Tandem Catalysis?

ACS Nano, Journal Year: 2023, Volume and Issue: 17(13), P. 12747 - 12758

Published: June 28, 2023

Electrochemically converting NO3- compounds into ammonia represents a sustainable route to remove industrial pollutants in wastewater and produce valuable chemicals. Bimetallic nanomaterials usually exhibit better catalytic performance than the monometallic counterparts, yet unveiling reaction mechanism is extremely challenging. Herein, we report an atomically precise [Ag30Pd4 (C6H9)26](BPh4)2 (Ag30Pd4) nanocluster as model catalyst toward electrochemical reduction (eNO3-RR) elucidate different role of Ag Pd site unveil comprehensive mechanism. Ag30Pd4 homoleptic alkynyl-protected superatom with 2 free electrons, it has metal core where 4 atoms are located at subcenter core. Furthermore, exhibits excellent eNO3-RR robust stability for prolonged operation, can achieve highest Faradaic efficiency NH3 over 90%. In situ Fourier-transform infrared study revealed that plays more critical NO2-, while makes major contribution catalyze NO2- NH3. The bimetallic adopts tandem rather synergistic effect eNO3-RR. Such finding was further confirmed by density functional theory calculations, they disclosed most preferable binding NO3-, which then binds water molecule release NO2-. Subsequently, transfer vicinal exposed promote formation.

Language: Английский

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Homonuclear dual-atom catalysts embedded on N-doped graphene for highly efficient nitrate reduction to ammonia: From theoretical prediction to experimental validation

Applied Catalysis B Environment and Energy, Journal Year: 2023, Volume and Issue: 339, P. 123156 - 123156

Published: Aug. 7, 2023

Language: Английский

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