Electrochemical Reduction Of CO2 Research Articles

Recent Advances in Urea Electrocatalysis: Applications, Materials and Mechanisms†

Comprehensive SummaryUrea plays a vital role in human society, which has various applications in organic synthesis, medicine, materials chemistry, and other fields. Conventional industrial urea production process is energy−intensive and environmentally damaging. Recently, electrosynthesis offers a greener alternative to efficient urea synthesis involving coupling CO2 and nitrogen sources at ambient conditions, which affords an achievable way for diminishing the energy consumption and CO2 emissions. Additionally, urea electrolysis, namely the electrocatalytic urea oxidation reaction (UOR), is another emerging approach very recently. When coupling with hydrogen evolution reaction, the UOR route potentially utilizes 93% less energy than water electrolysis. Although there have been many individual reviews discussing urea electrosynthesis and urea electrooxidation, there is a critical need for a comprehensive review on urea electrocatalysis. The review will serve as a valuable reference for the design of advanced electrocatalysts to enhance the electrochemical urea electrocatalysis performance. In the review, we present a thorough review on two aspects: the electrocatalytic urea synthesis and urea oxidation reaction. We summarize in turn the recently reported catalyst materials, multiple catalysis mechanisms and catalyst design principles for electrocatalytic urea synthesis and urea electrolysis. Finally, major challenges and opportunities are also proposed to inspire further development of urea electrocatalysis technology. Key ScientistsFor urea electrosynthesis, Furuya et al. firstly investigated the electrochemical coreduction of CO2 and NO3−/NO2− using gas‐diffusion electrodes in 1995. Then, Wang et al. effectively achieved C—N bond formation and urea synthesis on PdCu alloy nanoparticles in 2020. Shortly, Yan and Yu et al. proposed the formation of *CO2NO2 from *NO2 and *CO2 intermediates at early stage on In(OH)3 electrocatalyst in 2021, and employed defect engineering strategy to facilitate the *CO2NH2 protonation in 2022. Amal et al. Investigated the role that Cu‐N‐C coordination plays for both the CO2RR and NO3RR. After that, Zhang's group developed In‐based electrocatalysts with artificial frustrated Lewis pairs for urea, and they offered a systematic screening approach for catalyst design in urea electrosynthesis in 2023. And sargent et al. reported a strategy that increased selectivity to urea using a hybrid catalyst.For urea electrooxidation, Stevenson et al. investigated the effect of Sr substitution toward the urea oxidation reaction. Wang et al. provided insights into the urea electrooxidation process using a β‐Ni(OH)2 electrode and Qiao et al. elucidated a two‐stage reaction pathway for UOR in 2021.

Monolithic Nitrogen-Doped Carbon Electrode with Hierarchical Porous Structure for Efficient Electrochemical CO2 Reduction.

N-doped carbon materials have garnered extensive development in electrochemical CO2 reduction due to their abundant sources, high structural plasticity, and excellent catalytic performance. However, the use of powder carbon materials for electrocatalytic reactions limits their current density and mechanical strength, which pose challenges for industrial applications. In this study, we synthesized a monolithic N-doped carbon electrode with high mechanical strength for efficient electrochemical reduction of CO2 to CO through a simple pyrolysis method, using phenolic resin as the precursor and ZIF-8 as the sacrificial template. At 900 °C, the decomposition of ZIF-8 and the volatilization of Zn atoms promote the formation of a hierarchical porous structure in the carbon matrix, characterized by macropores with extended mesoporous channels. Simultaneously, N active species derived from ZIF-8 are effectively generated around the pores and fully exposed. The efficient mass transfer facilitated by the hierarchical porous structure and high activity of exposed nitrogen species enables efficient conversion of CO2 to CO. When the ZIF-8 content is 30%, the catalyst achieves a Faradaic efficiency of 88.9% for CO at a low potential of -0.7 V (vs RHE), with a CO production rate of 244.05 μmol h-1 cm-2. After 50 h of potentiostatic electrolysis, the current density and FECO remain stable. This work not only provides a strategy for the synergistic effects of hierarchical porous structures and nitrogen doping but also offers an effective method to avoid using powder binders and prepare integrated, stable monolithic electrodes.

Customizing Ionic Liquids Functionalized MOFs Composites with Hydrophobic Interface for Electrochemical CO2 Reduction.

The electrochemical carbon dioxide reduction reaction (CO2RR) to generate feedstocks for chemical products (e.g., carbon monoxide, CO) offers a highly attractive method for achieving the closure of the carbon cycle. Ionic liquids (ILs)-functionalized Cu-based catalyst Cu2O-HKUST-1/IL1/PTFE was developed, configuring metal-organic frameworks(MOFs) based materials with high adsorption and multiple active sites. The modified electrocatalysts exhibited high specific surface area, strong CO2 adsorption capacity, abundant active sites, and fast charge transfer rate. The nucleophilic active site of deprotonation at the C2 site in imidazole ILs further improved the selectivity of proton migration and CO product generation, which was verified through DFT calculations for the low Gibbs free energy of the generated intermediate interactions. In addition, the hydrophobic interface constructed by PTFE facilitated the inhibition of the hydrogen evolution reaction (HER) and significantly improved the efficiency of CO2 electroreduction. The Cu2O-HKUST-1/IL1/PTFE catalyst manifested a high C1 Faraday efficiency (FE) up to 96.5% and in particular 92.7% for FECO at -1.7 V vs RHE. The present work provides an efficient strategy for configuring ILs-functionalized MOFs-based materials with good hydrophobic interfaces to enhance the efficiency of CO2 electroreduction to C1 products.

Tuning the Inter‐Metal Interaction between Ni and Fe Atoms in Dual‐Atom Catalysts to Boost CO2 Electroreduction

AbstractDual‐atom catalysts (DACs) are promising for applications in electrochemical CO2 reduction due to the enhanced flexibility of the catalytic sites and the synergistic effect between dual atoms. However, precisely controlling the atomic distance and identifying the dual‐atom configuration of DACs to optimize the catalytic performance remains a challenge. Here, the Ni and Fe atomic pairs were constructed on nitrogen‐doped carbon support in three different configurations: NiFe‐isolate, NiFe‐N bridge, and NiFe‐bonding. It was found that the NiFe‐N bridge catalyst with NiN4 and FeN4 sharing two N atoms exhibited superior CO2 reduction activity and promising stability when compared to the NiFe‐isolate and NiFe‐bonding catalysts. A series of characterizations and density functional theory calculations suggested that the N‐bridged NiFe sites with an appropriate distance between Ni and Fe atoms can exert a more pronounced synergy. It not only regulated the suitable adsorption strength for the *COOH intermediate but also promoted the desorption of *CO, thus accelerating the CO2 electroreduction to CO. This work provides an important implication for the enhancement of catalysis by the tailoring of the coordination structure of DACs, with the identification of distance effect between neighboring dual atoms.

Atmosphere Induces Tunable Oxygen Vacancies to Stabilize Single‐Atom Copper in Ceria for Robust Electrocatalytic CO2 Reduction to CH4

Electrochemical carbon dioxide reduction (ECO2RR) shows great potential to create high‐value carbon‐based chemicals, while designing advanced catalysts at the atomic level remains challenging. The ECO2RR performance is largely dependent on the catalyst microelectronic structure that can be effectively modulated through surface defect engineering. Here, we provide an atmosphere‐assisted low‐temperature calcination strategy to prepare a series of single‐atomic Cu/ceria catalysts with varied oxygen vacancy concentrations for robust electrolytic reduction of CO2 to methane. The obtained Cu/ceria catalyst under H2 environment (Cu/ceria‐H2) exhibits a methane Faraday efficiency (FECH4) of 70.03% with a turnover frequency (TOFCH4) of 9946.7 h−1 at an industrial‐scale current density of 150 mA cm−2 in a flow cell. Detailed studies indicate the copious oxygen vacancies in the Cu/ceria‐H2 are conducive to regulating the surface microelectronic structure with stabilized Cu+ active center. Furthermore, density functional theory calculations and operando ATR‐SEIRAS demonstrate that the Cu/ceria‐H2 can markedly enhance the activation of CO2, facilitate the adsorption of pivotal intermediates *COOH and *CO, thus ultimately enabling the high selectivity for CH4 production. This study presents deep insights into designing effective electrocatalysts for CO2 to CH4 conversion by controlling the surface microstructure via the reaction atmosphere.

Atmosphere Induces Tunable Oxygen Vacancies to Stabilize Single-Atom Copper in Ceria for Robust Electrocatalytic CO2 Reduction to CH4.

Electrochemical carbon dioxide reduction (ECO2RR) shows great potential to create high-value carbon-based chemicals, while designing advanced catalysts at the atomic level remains challenging. The ECO2RR performance is largely dependent on the catalyst microelectronic structure that can be effectively modulated through surface defect engineering. Here, we provide an atmosphere-assisted low-temperature calcination strategy to prepare a series of single-atomic Cu/ceria catalysts with varied oxygen vacancy concentrations for robust electrolytic reduction of CO2 to methane. The obtained Cu/ceria catalyst under H2 environment (Cu/ceria-H2) exhibits a methane Faraday efficiency (FECH4) of 70.03 % with a turnover frequency (TOFCH4) of 9946.7 h-1 at an industrial-scale current density of 150 mA cm-2 in a flow cell. Detailed studies indicate the copious oxygen vacancies in the Cu/ceria-H2 are conducive to regulating the surface microelectronic structure with stabilized Cu+ active center. Furthermore, density functional theory calculations and operando ATR-SEIRAS demonstrate that the Cu/ceria-H2 can markedly enhance the activation of CO2, facilitate the adsorption of pivotal intermediates *COOH and *CO, thus ultimately enabling the high selectivity for CH4 production. This study presents deep insights into designing effective electrocatalysts for CO2 to CH4 conversion by controlling the surface microstructure via the reaction atmosphere.

Cation effect on the elementary steps of the electrochemical CO reduction reaction on Cu

Cation effect on the elementary steps of the electrochemical CO reduction reaction on Cu

Synthesis of Benzoic Acids from Electrochemically Reduced CO2 Using Heterogeneous Catalysts

A method for the synthesis of benzoic acids from aryl iodides using two of the most abundant and sustainable feedstocks, carbon dioxide (CO2) and water, is disclosed. Central to this method is an effective and selective electrochemical reduction of CO2 to CO, which mitigates unwanted dehalogenation reactions occurring when H2 is produced via the hydrogen evolution reaction (HER). In a 3‐compartment set‐up, CO2 was reduced to CO electrochemically by using a surface‐modified silver electrode in aqueous electrolyte. The ex‐situ generated CO further underwent hydroxycarbonylation of aryl iodides by MOF‐supported palladium catalyst in excellent yields at room temperature. The method avoids the direct handling of hazardous CO gas and gives a wide range of benzoic acid derivatives. Both components of the tandem system can be recycled for several consecutive runs while keeping a high catalytic activity.

Exploring C1-C3 variations and Fischer–Tropsch chemistry via electrochemical CO2 reduction on electrodeposited Cu/Ag and Ag/Cu electrodes

Ag and Cu bimetallic electrodes are extensively studied for producing C-C coupled C2+ reduction products through electrochemical CO2 reduction. In this study, we prepared electrodes with Cu electrodeposited on Ag supports (CuED/Ag) and Ag electrodeposited on Cu supports (AgED/Cu) via electrodeposition, demonstrating behaviors for reduction products under various electrochemical conditions. The products were categorized as H2, C1 (CO, CH4, formate, methanol), C2 (C2H4, ethanol, acetate, acetaldehyde, glycolaldehyde, and ethylene glycol), C3 (propanol, isopropanol), and Fischer–Tropsch (F-T) synthesis products (CnH2n and CnH2n+2, n ≥ 2). Notably, ethylene glycol was only observed over AgED/Cu. The reduction products dynamically changed with applied potentials and electrolyte concentrations. The mechanism was understood to involve surface H* adsorption, CO2 adsorption, C-C coupling, hydrogenation, and dehydration. Minor F-T synthesis chemistry was observed, explained by *CO and *CH2 insertion chain growth. The distinct product behaviors over the CuED/Ag and AgED/Cu electrodes provide valuable insights into the development of electrodes for producing value-added carbon products via CO2 utilization.

ZIF-8-derived carbon substrates embedded with atomically dispersed FeN2O2 active sites as bifunctional catalysts for electrochemical carbon dioxide and oxygen reduction

Transition metal assemblies on nitrogen-containing carbon substrates have promising applications as bifunctional electrocatalysts for electrochemical carbon dioxide reduction reaction (CO2RR) and oxygen reduction reaction (ORR). In this study, ZIF-8 with a rhombic dodecahedral morphology was grown from zinc nitrate and 2-methylimidazole feedstock. Then, a nitrogen-containing carbon substrate with a pore structure was formed after the release of Zn through high-temperature calcination. During the calcination process at 700°C, Fe atoms were physically adsorbed on the nitrogen-containing carbon substrate and ligated with N/O to form FeN2O2 reactive sites. For CO2RR, FeN2O2/NC exhibited excellent catalytic properties for converting CO2 to CO, achieving a high Faraday efficiency of 95.5 % at −0.7 V. Under alkaline conditions, it demonstrated ORR performance (E1/2 = 0.83 V) comparable with that of Pt/C (E1/2 = 0.82 V). This study not only presents an energy-efficient method for CO2RR but also provides new insights into highly active catalysts for ORR.

Tunable Ag-Ox coordination for industrial-level carbon-negative CO2 electrolysis

The electrochemical CO2 reduction (eCO2RR) is promising for eliminating CO2, generate valuable chemicals and utilize spare electricity. However, its industrialization is greatly hindered by low CO2 single-pass conversion efficiency (SPCE) in alkaline/neutral electrolytes, and poor compatibility between the electrolysis and intermittent energy system. Herein, a carbon-negative acidic eCO2RR system is developed using acidic-tolerant Ag based metal-organic frameworks (Ag-MOFs), achieving a high Faradaic efficiency of CO above 97 % in a broad working window of 10–400 mA cm−2 for unsaturated Ag-O2 clusters, and a high CO2 SPCE of 46.3 % even under industrial-level 400 mA cm−2. Being connected to solar cells, the acidic eCO2RR system displays a remarkable solar-to-chemical efficiency of 19.74 %, offering great potential for industrial eCO2RR directly driven by renewable energy. Specifically, the CO/HCOOH selectivity could be manipulated by adjusting the coordination number of Ag atoms in Ag-MOFs, and thus a Pourbaix-diagram is proposed to explain the tunable selectivity theoretically.

Rigidly Axial O Coordination-Induced Spin Polarization on Single Ni-N4-C Site by MXene Coupling for Boosting Electrochemical CO2 Reduction to CO.

Regulating the spin states in transition-metal (TM)-based single-atom catalysts (SACs), such as the TM-Nx-C configurations, is crucial for improving the catalytic activity. However, the role of spin in single Ni atoms facilitating the electrochemical CO2 reduction reaction (CO2RR) has been largely overlooked. Using first-principles simulations, we investigated the electrocatalytic performance of Ni-N4-C SACs vertically stacked on the O-terminated MXene nanosheets for the CO2RR. The terminated O atoms on MXene axially interact with the Ni atom due to significant charge transfer between them. Unlike the pure Ni-N4 site, which lacks spin polarization, the newly formed Ni-N4O configuration breaks the spin degeneracy of Ni d orbitals, dramatically lifting the energy level of spin-down d orbitals relative to that of spin-up d orbitals. As a result, the d electrons of Ni in the two spin channels are rearranged, leading to large net spin moments of 1.4 μB. Compared to the Ni-N4 site, the partially filled minority-spin dz2 orbitals of Ni on Ni-N4O weaken the occupied d-π* orbitals between Ni and *COOH, significantly stabilizing the key intermediate. The detailed reaction mechanisms and energetics show that four MXenes, namely, Hf3C2, Zr3C2, Hf2C, and Zr2C, can induce a large spin on the Ni site, thereby improving catalytic activity for CO2 reduction to CO, with a lower onset potential of about -0.75 V vs SHE compared to pure Ni SACs (-1.17 V) according to the potential-constant model with an explicit solvent environment.

Efficient and Selective Electrochemical CO2 to Formic Acid Conversion: A First-Principles Study of Single-Atom and Dual-Atom Catalysts on Tin Disulfide Monolayers.

Electrochemical CO2 reduction reaction (CO2RR) is a sustainable approach to recycle CO2 and address climate issues but needs selective catalysts that operate at low electrode potentials. Single-atom catalysts (SACs) and dual-atom catalysts (DACs) have become increasingly popular due to their versatility, unique properties, and outstanding performances in electrocatalytic reactions. In this study, we used Density Functional Theory along with the computational hydrogen electrode methodology to study the stability and activity of SACs and DACs by adsorbing metal atoms onto SnS2 monolayers. With a focus on optimizing the selective conversion of CO2 to formic acid, our analysis of the thermodynamics of CO2RR reveals that the Sn-SAC catalyst can efficiently and selectively catalyze formic acid production, being characterized by the low theoretical limiting potentials of -0.29 V. The investigation of the catalysts stability suggests that structures with low metal coverage and isolated metal centers can be synthesized. Bader analysis of charge redistribution during CO2RR demonstrates that the SnS2 substrate primarily provides the electronic charges for the reduction of CO2, highlighting the substrate's essential role in the catalysis, which is also confirmed by further electronic structure calculations.

Dynamically Stabilizing Oxygen Atoms in Silver Catalyst for Highly Selective and Durable CO2 Reduction Reaction.

Oxide derived catalyst displays outstanding catalytic activity and selectivity in electrochemical carbon dioxide reduction reaction (CO2RR), in which, it is found that residue oxygen atoms play a pivotal role in regulating the catalyst's electronic structure and thus the CO2RR process. Unfortunately, the intrinsic thermodynamic instability of oxygen atoms in oxide derived catalyst under cathodic CO2RR potentials makes it unstable during continuous electrolysis, greatly hindering its practical industrial applications. In this work, we develop a pulsed-bias technique that is able to dynamically stabilize the residue oxygen atoms in oxide derived catalyst during electrochemical CO2RR. As a result, the oxide derived catalyst under pulsed bias exhibits super catalytic stability in catalyzing electrochemical CO2RR, while keeping excellent catalytic activity and selectivity.

Increasing electrochemical carbon dioxide reduction to methane via a novel copper-based conductive metal organic framework

The development of a new system for the electrochemical carbon dioxide reduction reaction (ECO2RR) to methane (CH4) is challenging, and novel conductive metal organic frameworks (c-MOFs) for efficient ECO2RR to CH4 are critical to this system. Here, we report a novel c-MOF, copper-pyromellitic dianhydride-2-methylbenzimidazole (Cu-PD-2-MBI), in which the introduction of electron-withdrawing 2-methylbenzimidazole (2-MBI) into the copper-pyromellitic dianhydride (Cu-PD) interlayer elevated the valence of copper (Cu) ions, which improved the ECO2RR performance of Cu-PD-2-MBI. Cu-PD-2-MBI was tested in a flow cell, and the Faradaic efficiency of CH4 reached 73.7 %, with a corresponding partial current density of −428.3 mA·cm−2 at −1.3 V, which was higher than those of most reported Cu-based catalysts. Further exploration via theoretical calculations indicated that the intercalated 2-MBI in Cu-PD-2-MBI induced a shift in the d-band center in the Cu sites from −2.63 to −1.86 eV and reduced the formation energy of the *COOH and *CHO intermediates in the process of generating CH4 compared with those of the reference Cu-PD catalyst.

Nanowire arrays with abundant Cu–Ni interfaces for electroreduction of CO2 to ethylene

Electrochemical reduction of CO2 to ethylene (C2H4), driven by renewable electricity, represents a strategy for sustainable development and carbon neutrality. However, continuous production of C2H4 at high efficiency and low cost remains a significant challenge. Herein, a synergistic approach using non-precious metals was employed, and in situ construction of a nanoarray structure with abundant Cu–Ni interfaces (Ni/Cu NWs) on a gas diffusion layer (GDL) was performed. The atomic interactions at the interface significantly enhanced the efficiency of C–C coupling. The Faraday efficiency (FE) for C2H4 production reached 58.65 %, and the current density of 253.42 mA cm−2 at −1.1 V, markedly surpassing that of bare Cu nanowire (Cu NWs, 25.33 %). By virtue of the in-situ construction on the GDL, the Cu–Ni interface catalyst demonstrated excellent stability, operating under high current for more than 72 h. In situ infrared characterization and theoretical calculations demonstrate that the incorporation of Ni effectively enhanced the CO2 activation process, which is beneficial for the accumulation of key intermediate of C–C coupling. At the Cu–Ni interface, the energy barrier for C–C coupling was reduced, thereby effectively promoting the conversion of C2H4. This work presents a solution strategy for the interfacial engineering of non-precious metal catalysts.

A Universal Synthesis of Single-Atom Catalysts via Operando Bond Formation Driven by Electricity.

Single-atom catalysts (SACs), featuring highly uniform active sites, tunable coordination environments, and synergistic effects with support, have emerged as one of the most efficient catalysts for various reactions, particularly for electrochemical CO2 reduction (ECR). However, the scalability of SACs is restricted due to the limited choice of available support and problems that emerge when preparing SACs by thermal deposition. Here, an in situ reconstruction method for preparing SACs is developed with a variety of atomic sites, including nickel, cadmium, cobalt, and magnesium. Driven by electricity, different oxygen-containing metal precursors, such as MOF-74 and metal oxides, are directly atomized onto nitrogen-doped carbon (NC) supports, yielding SACs with variable metal active sites and coordination structures. The electrochemical force facilitates the in situ generation of bonds between the metal and the supports without the need for additional complex steps. A series of MNxOy (M denotes metal) SACs on NC have been synthesized and utilized for ECR. Among these, NiNxOy SACs using Ni-MOF-74 as a metal precursor exhibit excellent ECR performance. This universal and general SAC synthesis strategy at room temperature is simpler than most reported synthesis methods to date, providing practical guidance for the design of the next generation of high-performance SACs.

Electrolyte Composition‐Dependent Product Selectivity in CO2 Reduction with a Porphyrinic Metal–Organic Framework Catalyst

AbstractA copper porphyrin‐derived metal–organic framework electrocatalyst, FICN‐8, was synthesized and its catalytic activity for CO2 reduction reaction (CO2RR) was investigated. FICN‐8 selectively catalyzed electrochemical reduction of CO2 to CO in anhydrous acetonitrile electrolyte. However, formic acid became the dominant CO2RR product with the addition of a proton source to the system. Mechanistic studies revealed the change of major reduction pathway upon proton source addition, while catalyst‐bound hydride (*H) species was proposed as the key intermediate for formic acid production. This work highlights the importance of electrolyte composition on CO2RR product selectivity.

Theoretical investigation of sustainable CO2 electroreduction to high-value products utilizing N-doped/BN-modified Triphenylene-Graphdiyne catalysts

The potential of carbon-based triphenylene-graphdiyne (tpGDY) and its derivatives for the electrochemical CO2 reduction reaction (eCO2R) was comprehensively explored using density functional theory (DFT) calculations. Six variants were studied: pristine tpGDY, tpGDY-BN, tpGDY-N01, tpGDY-N02, tpGDY-N08, and tpGDY-BN-B01. Pristine tpGDY, tpGDY-BN, and tpGDY-N08 exhibited exceptional catalytic activity, efficiently converting CO2 into CO and HCOOH without external energy input. Significantly, N-doped tpGDY catalysts incorporating sp2-hybridized nitrogen atoms at the acetylenic sites (tpGDY-N01 and tpGDY-BN-N01) demonstrated remarkable electrocatalytic activity for the targeted conversion of CO2 to CH3OH. This outstanding performance is further corroborated by the low limiting potentials of −0.18 V and −0.27 V for tpGDY-N01 and tpGDY-BN-N01, respectively, highlighting their economic viability. Furthermore, the feasibility of C2 production (e.g., C2H5OH, C2H4 and C2H6) through C–C coupling of *CHO+*CO intermediate was investigated for tpGDY-N01 and tpGDY-BN-N01. DFT calculations suggest these pathways are achievable but require potentials of 0.84 V and 0.71 V for tpGDY-N01 and tpGDY-BN-N01, respectively. This study demonstrates the efficacy of N-doped tpGDY as a metal-free electrocatalyst for CO2 reduction, enabling the generation of both C1 and C2 products. This discovery holds significant promise for the advancement of sustainable CO2 conversion technologies.

Green synthesis of Cu-based metal organic framework for electrochemical CO2 conversion into formic acid

Metal-organic frameworks (MOFs) show promising amendments for the remediation of CO2. As the literature reports considerable progress in the electrochemical reduction of CO2, this work focuses on facile green synthesis of metal-organic framework and yields formic acid. The green synthesis MOF involved the use of an aqueous water-based solvent for synthesis, then compared with the conventional hydrothermal method of synthesis using N, N-Dimethylformamide (DMF), and was studied for electrochemical reduction of CO2. Green synthesis of copper benzene tricarboxylic acid (Cu BTC) and conventional synthesis of Cu BTC were characterized by XRD (X-ray diffraction), SEM (Scanning electron microscopy), TEM (Transition electron microscopy), FT-IR (Fourier transform infrared), and XPS (X-ray photoelectron spectroscopy). The performance of the green synthesis of Cu BTC resulted in the achievement of the highest FE (Faradic efficiency) of formic acid of 88 %, at - 0.6 V (vs. Reversible hydrogen electrode (RHE)) in 0.5 M Potassium chloride (KCl) electrolyte.