Search Results (61)

Electrocatalytic CO₂ reduction is a promising approach to mitigate rising atmospheric CO₂ levels while converting CO₂ into valuable products such as CH₄. Conversion into other useful substances further expands its potential applications. However, the efficiency of the CO₂ reduction reaction (CO₂RR) is strongly influenced by device geometry and CO₂ mass transfer in the electrolyte. In this work, we present and evaluate microchannel electrocatalytic devices consisting of a porous Cu cathode and a Pt anode, fabricated via metal-assisted chemical etching (MACE). The porous surfaces generated through MACE enhanced reaction activity. To study the impact of the distance between electrodes, several devices with different channel heights were fabricated and tested. The device with the highest CH₄ selectivity had a narrow inter-electrode gap of 50 μm and achieved a Faradaic efficiency of 56 ± 11% at an applied potential of −5 V versus an Ag/AgCl reference electrode. This efficiency was considerably higher than that of the device with larger inter-electrode gaps (300 and 480 μm). This reduced efficiency in the larger channel was attributed to limited CO₂ availability at the cathode surface. Bubble visualization experiments further demonstrated that the electrolyte flow rate had a strong impact on supplied CO₂ bubble morphology and mass transfer. At a flow rate of 0.75 mL/min, smaller CO₂ bubbles were formed, increasing the gas–liquid interfacial area and thereby enhancing CO₂ dissolution into the electrolyte. These results underline the critical role of electrode gap design and bubble dynamics in optimizing microchannel electrocatalytic devices for efficient CO₂RR. Full article

With the escalating challenges of global warming and the energy crisis, electrocatalytic CO₂ reduction reaction (CO₂RR) has emerged as a promising strategy to mitigate atmospheric CO₂ concentrations while converting it into high-value-added chemicals. Among various CO₂RR catalysts, copper-based materials exhibit unique capabilities for C-C coupling, yet their practical application remains constrained by several limitations: Low selectivity for C₂₊ products (typically <60%); Catalyst instability due to dynamic reconfiguration of active sites under high overpotentials; poor energy efficiency caused by competing hydrogen evolution reactions (HERs), etc. Recent studies demonstrate that nonmetallic heteroatom doping or functionalized ligand incorporation can effectively modulate the electronic structure and surface microenvironment of Cu-based catalysts, thereby enhancing CO₂RR performance. In this review, we comprehensively summarize recent advances in such strategies. We first systematically elucidate the unique advantages of copper-based catalysts as benchmark materials for multi-carbon (C₂₊) product synthesis, along with the current challenges they face. Subsequently, we highlight recent advances in modulating copper-based catalysts through the incorporation of diverse nonmetallic heteroatoms (e.g., N, S, B, P, halogens) or the introduction of functionalized ligands, with a particular focus on mechanistic insights and characterization methods aimed at enhancing C-C coupling efficiency and improving C₂₊ product selectivity. Finally, we present perspectives on the remaining opportunities and challenges in this research field. Full article

The renewable-energy-powered electrocatalytic CO₂ reduction reaction (CO₂RR) efficiently converts CO₂ into high-value chemicals and fuels, offering a promising approach to addressing environmental and energy sustainability challenges. This process is of immense significance for constructing a sustainable artificial carbon cycle. Cu-based catalysts exhibit remarkable catalytic activity and broad product selectivity in CO₂RR, which can be attributed to their excellent electrical conductivity, moderate adsorption energy, and unique electronic structure. This review comprehensively summarizes the advantages, practical applications, and mechanistic insights of Cu-based catalysts in CO₂RR, with a systematic based on recent advances in tuning strategies via electronic effects and structural design. Specifically, it emphasizes the influence of electronic structure tuning (electron-donating/-withdrawing effects and steric hindrance effects), active center tuning (single-atom catalysts, heterogeneous synergetic effects, and polymer modification), and surface structure (morphology effect, valence-state effect, and crystalline-facet effect) influences on catalytic performance. By rationally designing the catalyst structure, the adsorption behavior of reaction intermediates can be effectively regulated, thereby enabling the highly selective generation of target products. The objective of this paper is to provide a theoretical framework and actionable strategies for the structural design and catalytic performance optimization of Cu-based catalysts, with the ultimate goal of promoting the development and practical application of efficient CO₂RR catalytic systems. Full article

Electrocatalytic CO₂ reduction driven by renewable electricity offers a sustainable approach to producing valuable chemicals, though it is often hindered by low activity and selectivity. CuO, an important transition metal oxide, exhibits unique advantages in photoelectrocatalysis due to its high intrinsic catalytic activity and ability to serve as an active site for CO₂ reduction. SiO₂, a widely used substrate, facilitates Cu loading and increases the specific surface area of the catalyst. Meanwhile, g-C₃N₄ provides excellent visible-light responsiveness and efficient charge carrier mobility. Together, CuO, SiO₂, and g-C₃N₄ are earth-abundant, low-cost, and chemically stable, making them ideal for solar-to-fuel applications. Here, a novel ternary heterojunction photocatalyst was constructed using SiO₂, CuO, and g-C₃N₄. The heterostructure significantly improves light-harvesting efficiency, promotes efficient charge separation and transport, and simultaneously mitigates photogenerated carrier recombination and catalyst corrosion. The resulting SiO₂@CuO/g-C₃N₄ catalyst demonstrates outstanding CO₂ conversion performance, achieving a CO yield of 17 mmolg⁻¹h⁻¹ at 1.2 V_RHE with nearly 100% selectivity. Moreover, this work systematically investigates the electrocatalytic CO₂ reduction reaction (CO₂RR) mechanism on Cu-based catalysts, offering insights into the formation of high-value multicarbon products and highlighting the potential of rational heterojunction design in enhancing solar-driven fuel production efficiency. Full article

The advancement of efficient energy conversion and storage technologies is fundamentally linked to the development of electrochemical systems, including fuel cells, batteries, and electrolyzers, whose performance depends on key electrocatalytic reactions: hydrogen evolution (HER), oxygen evolution (OER), oxygen reduction (ORR), carbon dioxide reduction (CO₂RR), and nitrogen reduction (NRR). Beyond catalyst design, the electrolyte microenvironment significantly influences these reactions by modulating charge transfer, intermediate stabilization, and mass transport, making electrolyte engineering a powerful tool for enhancing performance. This review provides a comprehensive analysis of how fundamental electrolyte properties, including pH, ionic strength, ion identity, and solvent structure, affect the mechanisms and kinetics of these five reactions. We examine in detail how the electrolyte composition and individual ion contributions impact reaction pathways, catalytic activity, and product selectivity. For HER and OER, we discuss the interplay between acidic and alkaline environments, the effects of specific ions, interfacial electric fields, and catalyst stability. In ORR, we highlight pH-dependent activity, selectivity, and the roles of cations and anions in steering 2e⁻ versus 4e⁻ pathways. The CO₂RR and NRR sections explore how the electrolyte composition, local pH, buffering capacity, and proton sources influence activity and the product distribution. We also address challenges in electrolyte optimization, such as managing competing reactions and maximizing Faradaic efficiency. By comparing the electrolyte’s effects across these reactions, this review identifies general trends and design guidelines for enhancing electrocatalytic performance and outlines key open questions and future research directions relevant to practical energy technologies. Full article

The electrocatalytic CO₂ reduction reaction (CO₂RR) offers an energy-saving and environmentally friendly approach to producing hydrocarbon fuels. The use of a gas diffusion electrode (GDE) flow cell has generally improved the rate of CO₂RR, while the gas diffusion layer (GDL) remains a significant challenge. In this study, we successfully engineered a novel metal–organic framework (MOF) heterojunction through the controlled coating of zeolitic imidazolate framework (ZIF-L) on ultrathin nickel—metal–organic framework (Ni-MOF) nanosheets. This innovative architecture simultaneously integrates GDL functionality and exposes abundant solid–liquid–gas triple-phase boundaries. The resulting Ni-MOF@ZIF-L heterostructure demonstrates exceptional performance, achieving a formate Faradaic efficiency of 92.4% while suppressing the hydrogen evolution reaction (HER) to 6.7%. Through computational modeling of the optimized heterojunction configuration, we further elucidated its competitive adsorption behavior and electronic modulation effects. The experimental and theoretical results demonstrate an improvement in electrochemical CO₂ reduction activity with suppressed hydrogen evolution for the heterojunction because of its hydrophobic interface, good electron transfer capability, and high CO₂ adsorption at the catalyst interface. This work provides a new insight into the rational design of porous crystalline materials in electrocatalytic CO₂RR. Full article

Electrocatalytic CO₂ reduction reaction (CO₂RR) is a crucial technology for achieving carbon cycling and renewable energy conversion, yet it faces challenges such as complex reaction pathways, competition for intermediate adsorption, and low product selectivity. In recent years, molecular modification has emerged as a promising strategy. By adjusting the surface properties of catalysts, molecular modification alters the electronic structure, steric hindrance, promotes the adsorption of reactants, stabilizes intermediates, modifies the hydrophilic–hydrophobic environment, and regulates pH, thereby significantly enhancing the conversion efficiency and selectivity of CO₂RR. This paper systematically reviews the modification strategies and mechanisms of molecularly modified materials in CO₂RR. By summarizing and analyzing the existing literature, this review provides new perspectives and insights for future research on molecularly modified materials in electrocatalytic CO₂ reduction. Full article

Methane (CH₄) has attracted much attention regarding its use in electrochemical carbon dioxide reduction reaction (CO₂RR) due to its high mass-energy density; however, the uneven adsorption of intermediates on copper sites by conventional Cu-based catalysts limits the selective production of CH₄. The introduction of a second metal can effectively regulate the adsorption energy of intermediates on the Cu site. In this paper, a method of alloying Cu with oxyphilic metals (M) using rapid electrodeposition is presented; the synergistic effect of the bimetal effectively directed the reaction pathway toward CH₄. The best Faraday efficiency for methane occurred in the optimized Cu₃₀La₂₀ electrode, reaching 66.9% at −1.7 V vs. RHE potential. In situ infrared testing revealed that the *CHO intermediate—a critical species for the electrocatalytic conversion of CO₂ to CH₄—was detected on the Cu₃₀La₂₀ catalytic electrode. However, no *CHO intermediate was observed on the Cu₂₀La₃₀ electrode. Instead, the characteristic peak of the *OCCHO intermediate associated with C-C coupling emerged on the Cu₂₀La₃₀ catalyst. This indicates that the adsorbed oxygen-containing groups on lanthanum sites reacted with carbon-containing groups on copper sites to form C₂ products, serving as the primary reason for the shift in reduction products from methane to ethylene. Full article

The core challenge of integrated carbon capture and utilization (ICCU) technology lies in developing electrolytes that combine efficient carbon dioxide (CO₂) capture with electrocatalytic conversion capabilities. This review analyzes the structure–performance relationship between electrolyte properties and CO₂ electrochemical reduction (eCO₂RR), revealing the key regulatory mechanisms. Research shows that the performance of bicarbonate electrolytes heavily depends on the cation type, where Cs⁺ can achieve over 90% CO selectivity by suppressing the hydrogen evolution reaction (HER) and stabilizing reaction intermediates, though its strong corrosiveness limits practical applications. Although amine absorbents excel in carbon capture (efficiency > 90%), they tend to undergo competitive adsorption during electrocatalysis, making formic acid the primary product (FE = 15%); modifying electrodes with ionomers can enhance their activity by 1.15 times. Ionic liquids (ILs) demonstrate unique advantages due to their tunability: imidazolium-based ILs improve formate selectivity to 85% via carboxylate intermediate formation, while amino-functionalized task-specific ILs (TSILs) achieve a 1:1 stoichiometric CO₂ absorption ratio. Recent breakthroughs reveal that ternary IL hybrid electrolytes can achieve nearly 100% CO Faradaic efficiency (FE) through microenvironment modulation, while L-histidine additives boost CH₄ selectivity by 23% via interface modification. Notably, constructing a “bulk acidic–interfacial neutral” pH gradient system addresses carbonate deposition issues in traditional alkaline conditions, increasing C₂₊ product efficiency to 50%. Studies also highlight that cation–anion synergy (e.g., K⁺/I⁻) significantly enhances C-C coupling through electrostatic interactions, achieving 97% C₂₊ selectivity on Ag electrodes. These findings provide new insights for ICCU electrolyte design, with future research focusing on machine learning-assisted material optimization and reactor engineering to advance industrial applications. Full article

With the increase of CO₂ emissions caused by human activities, the development of efficient CO₂ reduction technology is crucial to help address the energy crisis and mitigate climate change. In this study, a series of Cu₃P/SnS₂ composites with varying Cu/Sn molar ratios were synthesized using a hydrothermal method to improve the activity and selectivity of the electrocatalytic reduction of CO₂ (CO₂RR). The successful synthesis and structural advantages of the composite were verified via XRD, XPS, SEM, TEM, and BET. Cu₃P/SnS₂-3 (Cu/Sn = 2:1) had the largest specific surface area (78.01 m² g⁻¹) and abundant active sites. The electrochemical performance test showed that in 0.1 M KHCO₃ electrolyte saturated with CO₂, the Faraday efficiency of Cu₃P/SnS₂-3 to CO reached 87% at −1.0 V potential, which was 29 times and 1.78 times higher than that of Cu₃P (3%) and SnS₂ (48.88%). In addition, the catalyst maintained a CO Faraday efficiency of more than 75% in a 5 h stability test. The mechanism study shows that the low Tafel slope, low charge transfer resistance, and high electrochemically active area of the composite significantly promote the CO₂RR kinetics. Full article

The electrocatalytic CO₂ reduction reaction (CO₂RR) into value-added multi-carbon C₂₊ products holds significant promise for sustainable chemical synthesis and carbon-neutral energy cycles. Among the various strategies developed to enhance CO₂RR, the use of ionic liquids (ILs) has emerged as a powerful approach for modulating the local microenvironment and electronic structure of Cu-based metal catalysts. In this study, to unravel the molecular-level mechanisms underlying these enhancements, density functional theory calculations (DFTs) were employed to systematically explore how ILs with different terminal groups modulate the electronic reconstruction of the Cu surface, further affecting the *CO–*CO coupling and product selectivity. Electronic structure analyses reveal that ILs bearing polar moieties (–SH, –COOH) can synergistically enhance the interfacial electron accumulation and induce an upshift of the Cu d-band center, thereby strengthening *CO adsorption. In contrast, nonpolar IL (CH₃) exhibits negligible effects, underscoring the pivotal role of ILs’ polarity in catalyst surface-state engineering. The free energy diagrams and transition state analyses reveal that ILs with polar groups significantly lower both the reaction-free energy and activation barrier associated with the *CO–*CO coupling step. This energetic favorability selectively inhibits the C₁ product pathways and hydrogen evolution reaction (HER), further improving the selectivity of C₂ products. These theoretical insights not only unveil the mechanistic origins of IL-induced performance enhancement but also offer predictive guidance for the rational design of advanced IL–catalyst systems for efficient CO₂ electroreduction. Full article

Electrocatalytic nitrate reduction reaction (NO₃⁻RR) to ammonia (NH₃) presents an alternative, sustainable approach to ammonia production. However, the existing catalysts suffer from poor NH₃ yield under lower concentrations of NO₃⁻, and the kinetic understanding of bimetal catalysis is lacking. In this study, a Co₃O₄–modified Cu₂₊₁O nanowire (CoCuNWs) catalyst with a high specific surface area was synthesized to effectively produce NH₃ from a 10 mM KNO₃ basic solution. CoCuNWs demonstrated a high NH₃ yield rate of 0.30 mmol h⁻¹ cm⁻² with an NH₃ Faradaic efficiency (FE) of 96.7% at −0.2 V vs. RHE, which is 1.5 times higher than the bare Cu₂₊₁O NWs. The synergistic effect between Co₃O₄ and Cu₂₊₁O significantly enhanced both the nitrate conversion and ammonia yield. Importantly, it is revealed that the surface of CoCuNWs is kinetically more easily saturated with NO₃⁻ (NO₂⁻) ions than that of Cu₂₊₁O NWs, as evidenced by both the higher current density and the plateau occurring at higher NO_x⁻ concentrations. In addition, CoCuNWs exhibit a higher diffusion coefficient of NO₃⁻, being 1.6 times higher than that of Cu₂₊₁O NWs, which also indicates that the presence of Co₃O₄ could promote the diffusion and adsorption of NO₃⁻ on CoCuNWs. Moreover, the ATR–SEIRAS analysis was applied to illustrate the reduction pathway of NO₃⁻ to NH₃ on CoCuNWs, which follows the formation of the key intermediate from *NO₂⁻, *NO, *NH₂OH to *NH₃. This work presents a strategy for constructing dual–metal catalysts for NO₃⁻RR and provides an insight to understand the catalysis from the perspective of the kinetics. Full article

Electrocatalytic nitrate reduction to ammonia (NO₃RR) is a promising approach to recycle nitrogen from nitrate pollutants, yet it remains challenged by low Faradaic efficiency and insufficient NH₃ production. Herein, Cu-doped nanoporous Co₂P (np-Co_2−xCu_xP) is reported as electrocatalyst for NO₃RR, achieving an ammonia yield rate of 30.6 mg h⁻¹ cm⁻² with a Faradaic efficiency of 93.4% at −0.3 V vs. RHE. In-situ spectroscopic analyses indicate that Cu incorporation modifies the surface electronic structure, resulting in the promotion of *H adsorption and *NO₂⁻ hydrogenation, thereby facilitating efficient ammonia generation. Full article

Under mild conditions, the effective conversion of carbon dioxide (CO₂) into formic acid (HCOOH) and carbon monoxide (CO) represents a promising avenue for mitigating greenhouse gas emissions and addressing energy crises. In this work, we analyzed the electro-catalytic activities of six metals (Ti, Fe, Ni, Cu, Zn, and Cr) anchored on monolayer molybdenum telluride (TM@MoTe₂) for the CO₂ reduction reaction (CO₂RR) from CO₂ to HCOOH and CO. Compared to the reversible hydrogen electrode, the limiting potential for HCOOH production on Ni@MoTe₂ is only about −0.38 V, and it is only about −0.20 V for the CO production on Cu@MoTe₂. The limiting potential is concerned with the free energies of *OCHO and *COOH. Both the CO₂RRs suppress the competing hydrogen evolution reaction (HER) and exhibit good selectivity for the desired reaction products. These features enable the efficient conversion of CO₂ into HCOOH on Ni@MoTe₂ or CO on Cu@MoTe₂. Our calculations could provide valuable insights for the design and synthesis of high-performance catalysts based on MoTe₂. Full article

In response to the detrimental impact of excessive fossil fuel usage on the environment and the looming energy crisis, the electrochemical reduction of carbon dioxide (CO₂RR) has emerged as a promising solution. This study investigates the potential of dual-atom catalysts, specifically boron (B) and transition metal (TM) co-modified C₉N₄, for efficient CO₂RR. The 2 × 2 × 1 supercell of C₉N₄, considering modification with 26 TM and B atoms, demonstrated stability, confirmed by binding and formation energy calculations. Molecular dynamics simulations further supported the thermal stability of the studied catalysts. The modified structures exhibited metallic behavior, suggesting potential facilitation of electron transfer during electroreduction. Furthermore, by conducting Gibbs free energy calculations on CO₂ reduction pathways, seven low overpotential catalysts were screened out. Considering the competitive hydrogen evolution reaction (HER), Sc-B and Hf-B demonstrate excellent selectivity towards CO₂, with Faradaic efficiencies (FE) close to 100%, and possess low limiting potentials of −0.30 and −0.53 eV, showcasing their potential to be excellent catalysts. The introduction of pre-adsorbed hydrogen atoms further optimized the advantage of CO₂RR over HER, with the efficiencies of Ti-B@C₉N₄-H and Hf-B@C₉N₄-H methods increasing from 0% and 28% to over 99%, respectively, providing new insights into overcoming the low selectivity of CO₂ reduction. Full article