Electrochemical Nitrate Reduction: Ammonia Synthesis and the Beyond

Advanced Materials, Journal Year: 2023, Volume and Issue: 36(17)

Published: June 9, 2023

Natural nitrogen cycle has been severely disrupted by anthropogenic activities. The overuse of N-containing fertilizers induces the increase nitrate level in surface and ground waters, substantial emission oxides causes heavy air pollution. Nitrogen gas, as main component air, used for mass ammonia production over a century, providing enough nutrition agriculture to support world population increase. In last decade, researchers have made great efforts develop processes under ambient conditions combat intensive energy consumption high carbon associated with Haber-Bosch process. Among different techniques, electrochemical reduction reaction (NO

Language: Английский

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Electronic Structure Design of Transition Metal-Based Catalysts for Electrochemical Carbon Dioxide Reduction

ACS Nano, Journal Year: 2024, Volume and Issue: 18(14), P. 9823 - 9851

Published: March 28, 2024

With the increasingly serious greenhouse effect, electrochemical carbon dioxide reduction reaction (CO2RR) has garnered widespread attention as it is capable of leveraging renewable energy to convert CO2 into value-added chemicals and fuels. However, performance CO2RR can hardly meet expectations because diverse intermediates complicated processes, necessitating exploitation highly efficient catalysts. In recent years, with advanced characterization technologies theoretical simulations, exploration catalytic mechanisms gradually deepened electronic structure catalysts their interactions intermediates, which serve a bridge facilitate deeper comprehension structure-performance relationships. Transition metal-based (TMCs), extensively applied in CO2RR, demonstrate substantial potential for further modulation, given abundance d electrons. Herein, we discuss representative feasible strategies modulate catalysts, including doping, vacancy, alloying, heterostructure, strain, phase engineering. These approaches profoundly alter inherent properties TMCs interaction thereby greatly affecting rate pathway CO2RR. It believed that rational design modulation fundamentally provide viable directions development toward conversion many other small molecules.

Language: Английский

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Coordination Environment Engineering of Metal Centers in Coordination Polymers for Selective Carbon Dioxide Electroreduction toward Multicarbon Products

ACS Nano, Journal Year: 2024, Volume and Issue: 18(9), P. 7192 - 7203

Published: Feb. 22, 2024

Electrocatalytic carbon dioxide reduction reaction (CO2RR) toward value-added chemicals/fuels has offered a sustainable strategy to achieve carbon-neutral energy cycle. However, it remains great challenge controllably and precisely regulate the coordination environment of active sites in catalysts for efficient generation targeted products, especially multicarbon (C2+) products. Herein we report engineering metal centers polymers electroreduction CO2 C2+ products under neutral conditions. Significantly, Cu polymer with Cu–N2S2 configuration (Cu–N–S) demonstrates superior Faradaic efficiencies 61.2% 82.2% ethylene respectively, compared selective formic acid on an analogous Cu–I2S2 mode (Cu–I–S). In situ studies reveal balanced formation atop bridge *CO intermediates Cu–N–S, promoting C–C coupling production. Theoretical calculations suggest that can induce electronic modulations sites, where d-band center is upshifted Cu–N–S stronger selectivity Consequently, displays trend while Cu–I–S favors due suppression couplings pathways large barriers.

Language: Английский

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Acidic conditions for efficient carbon dioxide electroreduction in flow and MEA cells

Chem Catalysis, Journal Year: 2023, Volume and Issue: 3(8), P. 100670 - 100670

Published: June 21, 2023

Language: Английский

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Simultaneous Defect and Size Control of Metal–Organic Framework Nanostructures for Highly Efficient Carbon Dioxide Electroreduction to Multicarbon Products

ACS Materials Letters, Journal Year: 2023, Volume and Issue: 5(8), P. 2121 - 2130

Published: July 11, 2023

Electrocatalytic carbon dioxide (CO2) reduction reaction (CO2RR) has offered a sustainable approach in converting an anthropogenic CO2 source to chemicals and fuels promote neutral. However, it remains challenging prepare high-performance catalysts for efficient selective electroreduction, especially toward the high-vaule multicarbon products. Here we report facile synthesis of four kinds nearly monodispersed CuTrz (HTrz = 1H,1,2,4-triazole) metal–organic framework (MOF) nanostructures with different sizes by controlling kinetics. Significantly, small demonstrate much superior CO2RR performance over large counterparts production neutral electrolytes, optimized Faradaic efficiency 55.4% 81.8% ethylene products, respectively. Detailed structural characterizations reveal that are polycrystalline rich grain boundaries, while ones single crystalline. This work highlights importance simultaneous defect size control MOFs boosting their production.

Language: Английский

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Electrochemical CO₂ Activation and Valorization on Metallic Copper and Carbon‐Embedded N‐Coordinated Single Metal MNC Catalysts

Angewandte Chemie International Edition, Journal Year: 2024, Volume and Issue: 63(21)

Published: March 12, 2024

Abstract The electrochemical reductive valorization of CO 2 , referred to as the CO2RR, is an emerging approach for conversion ‐containing feeds into valuable carbonaceous fuels and chemicals, with potential contributions carbon capture use (CCU) reducing greenhouse gas emissions. Copper surfaces graphene‐embedded, N‐coordinated single metal atom (MNC) catalysts exhibit distinctive reactivity, attracting attention efficient electrocatalysts CO2RR. This review offers a comparative analysis CO2RR on copper MNC catalysts, highlighting their unique characteristics in terms activation, C 1 /C 2(+) product formation, competing hydrogen evolution pathway. assessment underscores significance understanding structure–activity relationships optimize catalyst design selective Examining detailed reaction mechanisms structure‐selectivity patterns, explores recent insights changes chemical states, atomic motif rearrangements, fractal agglomeration, providing essential kinetic information from advanced in/ex situ microscopy/spectroscopy techniques. At end, this addresses future challenges solutions related today's disconnect between our current molecular structure–activity‐selectivity relations relevant factors controlling performance electrolyzers over longer times, larger electrode sizes, at higher densities.

Language: Английский

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Site‐selective Growth of fcc‐2H‐fcc Copper on Unconventional Phase Metal Nanomaterials for Highly Efficient Tandem CO₂ Electroreduction

Advanced Materials, Journal Year: 2024, Volume and Issue: 36(32)

Published: May 29, 2024

Abstract Copper (Cu) nanomaterials are a unique kind of electrocatalysts for high‐value multi‐carbon production in carbon dioxide reduction reaction (CO 2 RR), which holds enormous potential attaining neutrality. However, phase engineering Cu remains challenging, especially the construction unconventional Cu‐based asymmetric heteronanostructures. Here site‐selective growth on unusual gold (Au) nanorods, obtaining three kinds heterophase fcc‐2H‐fcc Au–Cu heteronanostructures is reported. Significantly, resultant Janus nanostructures (JNSs) break symmetric mode Au. In electrocatalytic CO RR, JNSs exhibit excellent performance both H‐type and flow cells, with Faradaic efficiencies 55.5% 84.3% ethylene products, respectively. situ characterizations theoretical calculations reveal co‐exposure 2H‐Au 2H‐Cu domains diversifies CO* adsorption configurations promotes spillover subsequent C–C coupling toward generation reduced energy barriers.

Language: Английский

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Electrocatalytic CO₂ Reduction for Dynamic C₁, C₂, and C₃₊ Chemistry over Electrodeposited Zn on Cu and CuZn Mesh Supports

Energy & Fuels, Journal Year: 2024, Volume and Issue: 38(16), P. 15497 - 15514

Published: July 30, 2024

The electrodeposition of Cu and Zn onto bare CuZn mesh supports offers a straightforward method for fabricating novel electrodes electrochemical CO2 reduction (EC CO2R). This study evaluates the performance these modified by assessing their Faradaic efficiency (FE) under various conditions including different electrolytes, concentrations, applied potentials, recycling effects, Nafion treatment. products were categorized into several groups: C1 gaseous (CO CH4), C2 (C2H4 C2H6), C3,4 hydrocarbons, major C1/C2/C3 liquid (formate, ethanol, propanol), minor (methanol, acetate, acetaldehyde, isopropanol). We evaluated dynamic FE variations experimental conditions. production C2+ hydrocarbons through EC CO2R was found to be analogous conventional Fischer–Tropsch synthesis, highlighting pivotal roles *CO *CHx intermediates. study's insights C1, C2, C3+ product chemistry aid in further development Cu-based electrocatalysts.

Language: Английский

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Electronic Structure Modulation of Unconventional Phase Metal Nanomaterials for Highly Selective Carbon Dioxide Electroreduction

ACS Materials Letters, Journal Year: 2023, Volume and Issue: 5(12), P. 3212 - 3221

Published: Nov. 6, 2023

The electrochemical carbon dioxide (CO2) reduction reaction (CO2RR) has been considered as a promising approach to convert atmospheric CO2 value-added chemicals promote neutrality. However, developing electrocatalysts with superior activity and high selectivity toward individual products remains great challenge. Herein we report the electronic structure modulation of unconventional phase metal nanomaterials achieve highly efficient electroreduction. It found that growing cerium oxide (CeOx) nanostructures on 4H/face-centered cubic (fcc) gold (Au) nanorods can significantly enhance their catalytic conversion monoxide. X-ray analysis indicates change 4H/fcc Au after CeOx overgrowth. In-situ attenuated total reflection infrared spectroscopy measurements reveal HCO3– concentration near surface Au-CeOx heteronanostructures is much higher than nanorods, facilitating process. Density functional theory calculations suggest activation effect nanorod for electrocatalytic CO2RR. synergy between promotes formation carboxyl (*COOH) species thus boosts CO2RR performance. This work highlights importance rational regulation unusual small molecules.

Language: Английский

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Acidic CO₂ electroreduction for high CO₂ utilization: catalysts, electrodes, and electrolyzers

Nanoscale, Journal Year: 2023, Volume and Issue: 16(5), P. 2235 - 2249

Published: Dec. 19, 2023

This minireview highlights recent advancements and perspectives on the electrochemical CO 2 reduction reactions (CO RR) in acidic environments, covering strategies from nanoscale to bulk scale.

Language: Английский

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