Search Results (119)

The electrochemical reduction of CO₂ (eCO2RR) has emerged as a promising route for carbon-neutral fuel and chemical production, offering a sustainable alternative to fossil-based processes. This article begins with an overview of conventional CO₂ conversion methods, highlighting their limitations and the advantages of electrochemical approaches under ambient conditions. We focus on recent advancements in electrocatalyst development for the eCO2RR, including metal-based, Cu-based, and metal-free catalysts. Metal-based catalysts are categorized by product selectivity (formate, CO, and multicarbon products), emphasizing their structures and practical performance. Cu-based catalysts are discussed in detail due to their unique capability to produce multicarbon products, with emphasis on design strategies, material types, and performance trends. Additionally, we review emerging metal-free catalysts, including their synthesis, mechanisms, and potential applications. This article provides a comparative analysis to guide future research toward efficient, selective, and durable catalysts for CO₂ electroreduction, aiming to accelerate the deployment of carbon capture and utilization technologies. Full article

Because the interfacial Cu⁰/Cu⁺ in Cu-based electrocatalyst promotes CO₂ electroreduction activity, it would be highly desirable to physically separate Cu-based nanoparticles through coating shells and load them onto porous carriers. Herein, multilayered graphene-coated Cu (Cu@G) nanoparticles with tailorable core diameters (28.2–24.2 nm) and shell thicknesses (7.8–3.0 layers) were fabricated via lased ablation in liquid. A thin Cu₂O layer was confirmed between the interface of the Cu core and the graphene shell, providing an interfacial Cu⁰/Cu⁺. Cu@G cross-linked biochars (Cu@G/Bs) with developed porosity (31.8–155.9 m²/g) were synthesized. Morphology, crystalline structure, porosity, and elemental chemical states of Cu@G and Cu@G/Bs were characterized. Cu@G/Bs captured CO₂ with a maximum sorption capacity of 107.03 mg/g at 0 °C. Furthermore, 95.3–97.1% capture capacity remained after 10 cycles. Cu@G/Bs exhibited the most superior performance with 40.7% of FE_C2H4 and 21.7 mA/cm² of current density at −1.08 V vs. RHE, which was 1.7 and 2.7 times higher than Cu@G. Synergistic integration of developed porosity for efficient CO₂ capture and the fast charge transfer rate of interfacial Cu₂O/Cu enabled this improvement. Favorable long-term stability of the phase/structure and CO₂ electroreduction activity were present. This work provides new insight for integrating Cu@G and a biochar platform to efficiently capture and electro-reduce CO₂. 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

The electrochemical reduction of carbon monoxide (COER) offers a promising route for generating value-added multi-carbon (C₂₊) products, such as ethanol, but achieving high catalytic performance remains a significant challenge. Herein, we performed comprehensive density functional theory (DFT) computations to evaluate CO-to-ethanol conversion on single metal atoms anchored on graphitic carbon nitride (TM/g–CN). We showed that these metal atoms stably coordinate with edge N sites of g–CN to form active catalytic centers. Screening 20 TM/g–CN candidates, we identified V/g–CN and Zn/g–CN as optimal catalysts: both exhibit low free-energy barriers (<0.50 eV) for the key ^*CO hydrogenation steps and facilitate C–C coupling via an Eley–Rideal mechanism with a negligible kinetic barrier (~0.10 eV) to yield ethanol at low limiting potentials, which explains their superior COER performance. An analysis of d-band centers, charge transfer, and bonding–antibonding orbital distributions revealed the origin of their activity. This work provides theoretical insights and useful guidelines for designing high-performance single-atom COER catalysts. Full article

Reducing atmospheric carbon dioxide is a critical global priority. This study investigates the influence of Cu-Ni nanoalloy loading on the CO₂ electroreduction efficiency in the context of mesoporous carbon supports. Current methods struggle when it comes to catalyst efficiency, selectivity, and longevity. By synthesizing copper–nickel nanoparticles through chemical reduction and depositing them on porous carbon, this research aimed to optimize catalyst loading and understand the structure–activity relationships. Catalyst performance was evaluated using chronoamperometry and linear sweep voltammetry (LSV). The results showed that 12 wt% catalyst loading achieved optimal CO₂ reduction, outperforming its 36 wt% counterpart by balancing the catalyst quantity. This study reveals that 12 wt% Cu-Ni loading provides a higher CO₂ reduction current density and greater long-term stability than 36 wt% loading, owing to better nanoparticle dispersion and reduced aggregation. Unlike previous Cu-Ni/mesoporous carbon studies, this work uniquely compares different loadings to directly correlate the structure, electrochemical performance, and catalyst durability. Full article

The galvanostatic electrodeposition of zinc on carbon paper from mildly acidic solutions (ZnCl₂: 0.05–0.1 M; H₃BO₃: 0.05 M) was investigated. The deposits’ growth mechanisms were analyzed through the study of the electrodeposition potential transients and the physical characterization of the electrodes synthesized by varying the current density, transferred charge, and zinc precursor concentration. The analysis reveals that the transition from crystalline to amorphous mossy deposits takes place via the electrodeposition of metallic zinc followed by the formation of oxidized zinc structures. The time required for this transition can be controlled by varying the zinc precursor concentration and electrodeposition current density, allowing for the synthesis of composite zinc/oxidized zinc electrodes with varying ratios of the oxidized to underlying metallic phases. The impact of this ratio on the electrode activity for CO₂ electroreduction is analyzed, highlighting that composite zinc/oxidized zinc electrodes can achieve a faradaic efficiency to CO equal to 82% at −1.8 V vs. Ag/AgCl. The mechanisms behind the variations in the catalytic activity with varying morphologies and structures are discussed, providing guidelines for the synthesis of composite zinc/oxidized zinc electrodes for CO₂ electroreduction. Full article

Co(II) complexes have shown promising applications as single-molecule magnets (SMMs) in quantum computing and structural biology. Deciphering the Co(II) complexes may facilitate the development of SMM materials. Structural optimizations and calculations of chemical and magnetic properties were performed for Co(II) complexes with a tripodal tetradentate phenolate-amine ligand using MP2/aug-cc-pvdz, MP2/Def2svp, and CASSCF/Def2svp methods. The Second Order Perturbation Theory Analysis of Fock Matrix in NBO Basis unravels that Co(II) ions form unusual coordinate quasi-double bonds with ligand oxygen donor atoms, and the bond strengths range from 142.01 kcal/mol to 167.36 kcal/mol but lack further spectrometric evidence. The average 151.70 kcal/mol of the Co(II-O coordinates quasi-double bonds are formed mainly by two lone pairs of electrons from the ligand phenolate donor oxygen atoms. Dispersion forces contribute 24%, 28%, 27%, and 31% to the Co(II)-ligand interaction. Theoretical results of ZFS D, transversal ZFS E, and g-factor agree well with the experimental values. Magnetic susceptibility parameters calculated based on 5 doublet roots account for 85% of results computed 40 doublet roots are specified. These insights may aid in the rational design of SMM materials and Co(II) porphyrin fullerene conjugate for CO₂ electroreduction with superior magnetic properties. 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

In this study, we designed and synthesized a series of chromium-based polymers (Cr-Ps) and their composites using oxidized carbon nanotubes (O-CNTs) through one-pot ligand engineering. The H₂O₂ production capacity of Cr-Ps increased with an increasing ratio of C–O and Cr–O bonds, which is consistent with the trend observed in the Cr-Ps@O-CNT. The addition of O-CNTs during Cr-Ps synthesis led to a dense structure, which enhanced the electron donor effect and effectively improved the selectivity of the materials for the electrocatalytic production of H₂O₂. Furthermore, during the modulation of different ligands, we observed that the polymers and their complexes formed with terephthalic acid ligands containing para-carboxyl groups had the highest coordination activity and selectivity. The Cr-BDC@O-CNT, using terephthalic acid as the ligand, had the highest C–O and Cr–O densities, resulting in an H₂O₂ yield of 87% in an alkaline solution and an electron transfer number of about 2.2. Compared with Cr-BDC without O-CNTs, its selectivity increased by 32%, due to the higher number of C–O and Cr–O bonds in its dense structure. Moreover, the mass activity of the Cr-BDC@O-CNT reached 19.42 A g⁻¹ at 0.2 V and the Faraday efficiency reached up to 94%, demonstrating excellent electroreduction activity. Our work provides insight into the design of efficient H₂O₂ electrocatalysts through ligand engineering, opening up new ideas for future research. 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

The conversion of CO₂ through the electrochemical reduction reaction (ECO₂RR) into chemicals or fuels is regarded as one of the effective ways to decrease atmospheric CO₂ concentrations. In this study, a Cu-Sn bimetallic electrocatalyst (ER-Sn_mCu_nO_x-t/CC) was successfully prepared via a chemical foaming method and electrochemical reduction. SEM showed that ER-Sn₁Cu₁O_x-500 nanoparticles were uniformly distributed on the carbon cloth, which benefited from foaming. The XPS results demonstrated the synergistic interaction between Cu and Sn and the existence of oxygen vacancies originating from the electroreduction. Due to the above features, ER-Sn₁Cu₁O_x-500/CC achieved 84.1% FE for HCOOH at −1.1 V vs. RHE, and the corresponding J_HCOOH was up to 32.4 mA·cm⁻² in the H-type cell. Especially in the flow cell, ER-Sn₁Cu₁O_x-500/GDE could reach a high J_HCOOH of 190 mA·cm⁻² at −1.1 V vs. RHE and maintained J_HCOOH higher than 100 mA·cm⁻² for 24 h with a formic acid selectivity over 70%, indicating both excellent catalytic activity and high HCOOH selectivity. In situ FTIR results revealed that synergism between Cu and Sn could regulate the adsorption of intermediates, thus enhancing the catalytic performance of ER-Sn₁Cu₁O_x-500 for ECO₂RR. Full article

CO₂ electrochemical reduction is a promising way to convert CO₂ to valuable fuels and chemicals. This study presents a porous Cu@Zn foam catalyst with a tailored hydrophobic surface for enhanced CO₂ reduction. The catalyst is synthesized via a modified dynamic hydrogen bubble template method, incorporating polytetrafluoroethylene (PTFE) during electrodeposition to control wettability. This strategy creates a hydrophobic microenvironment that significantly increases the three-phase (gas–liquid–solid) contact area, promoting CO₂ mass transfer and suppressing the competing hydrogen evolution reaction. The optimized Cu@Zn-8PTFE catalyst achieves a CO Faraday efficiency (FE_CO) of 87.53% at −35 mA cm⁻², a 40% improvement over the unmodified Cu@Zn. Furthermore, it also exhibits excellent stability, maintaining FE_CO > 90% for 64 h at −15 mA cm⁻². While hydrophobic modification is beneficial, excess PTFE loading reduces performance by covering active sites and diminishing the three-phase interface. This work highlights the importance of controlling catalyst wettability to optimize the three-phase interface for enhanced CO₂ electroreduction. Full article

Currently, the electrochemical reduction of carbon dioxide faces significant challenges, including poor selectivity for C₂ products and low conversion efficiency. An effective strategy for optimizing the reduction reaction pathway and enhancing catalytic performance involves manipulating highly unsaturated atomic sites on the catalyst’s surface, thereby increasing the number of active sites. In this study, we employed sodium dodecylbenzenesulfonate (SDBS) as a surfactant in the electrodeposition method to synthesize copper cubes encapsulated with an amorphous shell (100 nm–250 nm) containing numerous defect sites on its surface. The electrocatalytic CO₂ reduction reactions in an H-type reactor showed that, compared to ED-Cu synthesized without additives, AS (amorphous shell)-Cu-5 exhibited a Faradaic efficiency value for ethylene that was 1.7 times greater than that of ED-Cu while significantly decreasing the Faradaic efficiency of hydrogen production. In situ attenuated total reflectance surface-enhanced infrared spectroscopy (ATR-SEIRAS) revealed that introducing an amorphous shell and abundant defects altered both the intermediate species and reaction pathways on the AS-Cu-5 catalyst’s surface, favoring C₂H₄ formation. The density functional theory (DFT) calculations further confirmed that amorphous copper lowers the energy barrier required for C-C coupling, resulting in a marked enhancement in FE-C₂H₄. Therefore, additive-assisted electrodeposition presents a simple and rapid synthesis method for improving ethylene selectivity in copper catalysts. 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

The electrochemical CO₂ reduction (eCO₂RR) to valuable chemicals offers a promising method to combat global warming by recycling carbon. Among the possible products, syngas—a CO and H₂ mixture—is especially valuable for industrial reactions. The use of Room Temperature Ionic Liquids (RTILs) electrolytes presents a promising pathway for eCO₂RR because of the lower overpotential required and the increased CO₂ solubility with respect to the aqueous ones. Ensuring a constant CO/H₂ production is essential, and it relies on both the catalyst and reactor design. This study explores eCO₂RR in RTIL mixtures of 1-butyl-3-methyl imidazolium trifluoromethanesulfonate (good for CO₂ conversion) and 1-butyl-3-methyl imidazolium acetate (good for CO₂ capture), with various amounts of water as a proton source. We evaluated syngas production stability across different electrochemical cells and ion exchange membranes after determining the appropriate electrolyte mixture for a suitable CO/H₂ ratio near 1:1. The two-chamber cell configuration outperformed single-cell designs by reducing oxidative RTILs degradation and by-products formation. Using a bipolar membrane (BPM) in forward mode led to catholyte acidification, causing an increase of HER relative to eCO₂RR over time, confirmed by Multiphysics modeling. Conversely, an anionic exchange membrane (AEM) maintained constant syngas production over extended periods. This work offers guidelines for syngas generation in RTIL-based systems from waste-CO₂ reduction, which can be useful for other green chemical synthesis processes. Full article