A Copper–Zinc Cyanamide Solid-Solution Catalyst with Tailored Surface Electrostatic Potentials Promotes Asymmetric N-Intermediate Adsorption in Nitrite Electroreduction

Journal of the American Chemical Society, Год журнала: 2025, Номер 147(9), С. 8012 - 8023

Опубликована: Фев. 18, 2025

The electrocatalytic nitrite reduction (NO2RR) converts nitrogen-containing pollutants to high-value ammonia (NH3) under ambient conditions. However, its multiple intermediates and multielectron coupled proton transfer process lead low activity NH3 selectivity for the existing electrocatalysts. Herein, we synthesize a solid-solution copper-zinc cyanamide (Cu0.8Zn0.2NCN) with localized structure distortion tailored surface electrostatic potential, allowing asymmetric binding of NO2-. It exhibits outstanding NO2RR performance Faradaic efficiency ∼100% an yield 22 mg h-1 cm-2, among best such process. Theoretical calculations in situ spectroscopic measurements demonstrate that Cu-Zn sites coordinated linear polarized [NCN]2- could transform symmetric [Cu-O-N-O-Cu] CuNCN-NO2- [Cu-N-O-Zn] configuration Cu0.8Zn0.2NCN-NO2-, thus enhancing adsorption bond cleavage. A paired electro-refinery Cu0.8Zn0.2NCN cathode reaches 2000 mA cm-2 at 2.36 V remains fully operational industrial-level 400 >140 h production rate ∼30 mgNH3 cm-2. Our work opens new avenue tailoring potentials using strategy advanced electrocatalysis.

Язык: Английский

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Pd Nanoparticle Size‐Dependent H^* Coverage for Cu‐Catalyzed Nitrate Electro‐Reduction to Ammonia in Neutral Electrolyte

Small, Год журнала: 2024, Номер 20(46)

Опубликована: Авг. 3, 2024

Abstract Electrochemical conversion of nitrate (NO 3 − ) to ammonia (NH is an effective approach reduce pollutants in the environment and also a promising low‐temperature, low‐pressure method for synthesis. However, adequate H * intermediates are highly expected NO hydrogenation, while suppressing competitive hydrogen evolution. Herein, effect coverage on RR synthesis by Cu electrocatalysts investigated. The can be adjusted changing Pd nanoparticle sizes. optimized Pd@Cu with average size 2.88 nm shows best activity RR, achieving maximum Faradaic efficiency 97% (at −0.8 V vs RHE) NH yield 21 mg h −1 cm 2 , from industrial wastewater level 500 ppm – . In situ electrochemical experiments indicate that particles promote hydrogenation via well‐modulated adsorbed species. Coupling anodic glycerol oxidation reaction, ammonium formate successfully obtained as value‐added products membrane electrode assembly electrolyzer. This work provides feasible strategy obtaining size‐dependent hydrogenation.

Язык: Английский

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Industrial‐current Ammonia Synthesis by Polarized Cuprous Cyanamide Coupled to Valorization of Glycerol at 4,000 mA cm⁻²

Advanced Materials, Год журнала: 2025, Номер unknown

Опубликована: Фев. 21, 2025

Abstract The electrocatalytic nitrate reduction (NO 3 RR) holds significance in both NH synthesis and contamination remediation. However, achieving industrial‐scale current high stability membrane electrode assembly (MEA) electrolyzer remains challenging due to inherent full‐cell voltage for sluggish NO RR water oxidation. Here, Cu 2 NCN with positive surface electrostatic potential V S (r) is applied as highly efficient electrocatalysts achieve industrial‐current low‐voltage stable production MEA coupled anodic glycerol This paired electro‐refinery (PER) system reaches 4000 mA cm −2 at 2.52 industrial‐level 1000 100 h the rate of 97000 µg NH3 −1 a Faradaic efficiency 83%. Theoretical calculations elucidate that asymmetric electron‐withdrawing [N−C≡N] units enhance polarization (r), promoting robust adsorption * on facilitate O−N bond dissociation. A comprehensive techno‐economic analysis demonstrates profitability commercial viability this system. Our work opens new avenue marks significant advancement systems industrial synthesis.

Язык: Английский

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A novel 2D Co0.63Te nanosheets for a high-performance hybrid asymmetric supercapacitor and hydrogen evolution reaction

Journal of Energy Storage, Год журнала: 2024, Номер 101, С. 113860 - 113860

Опубликована: Сен. 29, 2024

Язык: Английский

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Rapid synthesis of PtRu nanoparticles on aniline-modified SWNTs in EMSI engineering for enhanced alkaline water electrolysis

Journal of Power Sources, Год журнала: 2025, Номер 631, С. 236297 - 236297

Опубликована: Янв. 25, 2025

Язык: Английский

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Surface Anticorrosion Engineering by Polyphosphate Oxyanions for Durable Seawater Oxidation

Advanced Energy Materials, Год журнала: 2024, Номер unknown

Опубликована: Авг. 29, 2024

Abstract Electrolysis of seawater represents great potentials for sustainable hydrogen production. However, both competitive Cl − adsorption and catalysts corrosion caused by chlorine oxidation reaction (ClOR) are major challenges in electrolysis. Inspired the concept hard soft acids bases (HSAB), polyphosphate oxyanions (P 3 O 10 5− ) on Ni(OH) 2 surface is coordinated to obtain harder acid Ni sites, which could 160 times stability enhancement compared pure oxygen evolution (OER) alkaline at 800 mA cm −2 . Also, turnover frequency value ‐P 50 that , implying higher intrinsic OER activity Theoretical experimental investigations show P facilitate transition 3+ >3+ thus preferring base OH rather than This enhance selectivity inhibit undesirable ClOR. Furthermore, molecular dynamics simulations indicate concentration near electrode be reduced nearly half due electrostatic repulsion oxyanions. When assembled into an electrolyzer splitting, it operate 2.2 V with large current up 1.4 A 240 h.

Язык: Английский

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Key Strategies for Continuous Seawater Splitting for Hydrogen Production: From Principles and Catalyst Materials to Electrolyzer Engineering

Advanced Functional Materials, Год журнала: 2024, Номер 34(45)

Опубликована: Авг. 27, 2024

Abstract Due to the high cost of ultra‐pure water supply and mismatch between sources renewable energy distribution, large‐scale production green hydrogen through seawater electrolysis has generated significant interest. This presents an attractive potential technology within framework carbon‐neutral production. However, owing complex composition seawater, particularly competitive oxidation reactions corrosion issues involving Cl − , suffered from low selectivity poor stability in oxygen evolution reaction (OER), which severely impact efficiency hinder practical applications. To further promote in‐depth research applications electrolysis, this review introduces principles, key advantages, challenges electrolysis. Specifically, design strategies are categorized for highly active OER electrocatalysts including catalyst design, chemical systems, other special process design. ensure long‐term operational various such as employing self‐supporting materials, surface protection strategies, electrolyzer discussed. Finally, current future prospects industrialization proposed It is expected that provides new insights seawater‐based future.

Язык: Английский

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Engineering the Sandwich‐Type Porphyrinic MOF‐Ruthenium–Nickel Foam Electrode for Boosting Overall Water Splitting via Self‐Reconstruction

Small Methods, Год журнала: 2024, Номер unknown

Опубликована: Сен. 9, 2024

Abstract The rational construction of a hierarchical noble metal–metal‐organic frameworks (MOFs) structure is anticipated to yield enduring and highly efficient performance in alkaline electrocatalytic water splitting. Herein, sandwich strategy employed enhance the stability, wherein active RutheniRu (Ru) nanosheets are incorporated onto nickel foam (NF) subsequently covered with porphyrinic MOFs (PMOFs). In addition, activated PMOF‐NiOOH‐Ru 20 /NF‐C/A electrodes obtained by electrochemical self‐reconstruction as cathode anode, respectively. Density functional theory (DFT) calculations demonstrated that resulting heterointerface effectively facilitated electron transfer, enhanced H 2 O adsorption capacity, optimized Δ G values for * OOH. Consequently, exhibited low overpotentials hydrogen evolution reaction (HER) oxygen (OER), accompanied minimal Ru leakage. Furthermore, stable overall splitting can be achieved voltage 1.456 V@10 mA cm −2 over 120 h. Even when operated simulated seawater, prepared similar activity stability. This study contributes deeper understanding regulation mechanism stability sites process.

Язык: Английский

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Reversible Hydrogen Acceptor–Donor Enables Relay Mechanism for Nitrate‐to‐Ammonia Electrocatalysis

Angewandte Chemie, Год журнала: 2024, Номер unknown

Опубликована: Окт. 21, 2024

Abstract Electrocatalytic nitrate reduction is a crucial process for sustainable ammonia production. However, to maximize yield efficiency, this technology inevitably operates at the potentials more negative than 0 V vs. RHE, leading high energy consumption and competitive hydrogen evolution. To eradicate issue, tungsten bronze (H x WO 3 ) as reversible donor‐acceptor partnered with copper (Cu) enable relay mechanism positive which involves rapid intercalation of H into lattice, prompt de‐intercalation lattice transfer onto Cu, spontaneous H‐mediated nitrate‐to‐ammonia conversion on Cu. The resulting catalysts demonstrated rate 3332.9±34.1 mmol g cat −1 h Faraday efficiency ~100 % 0.10 displaying record‐low estimated 17.6 kWh kg . Using these catalysts, we achieve continuous production in an enlarged flow cell real 17.0

Язык: Английский

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Reversible Hydrogen Acceptor–Donor Enables Relay Mechanism for Nitrate‐to‐Ammonia Electrocatalysis

Angewandte Chemie International Edition, Год журнала: 2024, Номер unknown

Опубликована: Окт. 21, 2024

Electrocatalytic nitrate reduction is a crucial process for sustainable ammonia production. However, to maximize yield efficiency, this technology inevitably operates at the potentials more negative than 0 V vs. RHE, leading high energy consumption and competitive hydrogen evolution. To eradicate issue, tungsten bronze (H

Язык: Английский

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