Electrochemical Reduction Of CO2 Research Articles

Effects of carbon support ozonation on the electrochemical reduction of CO2 to formate and syngas in a flow cell on Pd nanostructures

Pd convers electrochemically CO2 into formate at the most positive known potentials but with low activity. Additionally, Pd is CO selective at more negative potentials, but is poisoned by the strongly bound CO∗ intermediate. Improving the activity and stability of Pd-based electrocatalysts holds promise for improving the electrochemical production of formic acid. Herein, we studied the effects of carbon support and its ozonation on the selectivity of electrochemical CO2 reduction on Pd. The ozone treatment is found to improve the activity and formate selectivity at low overpotentials on single-walled carbon nanotube-supported catalysts with partial current densities up to −12 mA cm−2 in 0.5 M KHCO3 at potentials of −0.35 V and −0.45 V (vs. RHE). At more negative potentials, the catalysts become more selective towards CO and an opposite trend for CO-selectivity and ozonation duration is demonstrated. Unfortunately, the materials show deactivation in the form of decreased formate selectivity and increased hydrogen and CO evolution, especially when supports treated with ozone for a longer duration. The results and possible mechanisms are discussed based on previous findings and the physicochemical characterizations of the prepared catalysts. This work shows that a simple ozone treatment of carbons changes the efficiency of CO2 electroreduction.

Electrochemical Formation of C2+ Products Steered by Bridge-Bonded *CO Confined by *OH Domains.

During the electrochemical CO2 reduction reaction (eCO2RR) on copper catalysts, linear-bonded CO (*COL) is commonly regarded as the key intermediate for the CO-CO coupling step, which leads to the formation of multicarbon products. In this work, we unveil the significant role of bridge-bonded *CO (*COB) as an active species. By combining in situ Raman spectroscopy, gas and liquid chromatography, and density functional theory (DFT) simulations, we show that adsorbed *OH domains displace *COL to *COB. The electroreduction of a 12CO+13CO2 cofeed demonstrates that *COB distinctly favors the production of acetate and 1-propanol, while *COL favors ethylene and ethanol formation. This work enhances our understanding of the mechanistic intricacies of eCO(2)RR and suggests new directions for designing operational conditions by modifying the competitive adsorption of surface species, thereby steering the reaction toward specific multicarbon products.

Enhanced Local CO Coverage on Cu Quantum Dots for Boosting Electrocatalytic CO2 Reduction to Ethylene

AbstractEthylene (C2H4) electrosynthesis from the electrocatalytic CO2 reduction process holds enormous potential applications in industrial production. However, the sluggish kinetics of C─C coupling often result in low yield and poor selectivity for C2H4 production. Herein, the performance of Cu catalysts of varying sizes is investigated, prepared via a cryo‐mediated liquid phase exfoliation technique, for the electrochemical CO2 reduction to C2H4. The activity and selectivity of C2H4 gradually increase as the size of the Cu catalysts decreases from tens of nanometers to a few nanometers. Impressively, the 5 nm Cu quantum dots (Cu‐5) achieve a maximum C2H4 Faradaic efficiency (FE) of 81.5% and a half‐cell cathodic energy efficiency (CEE) of 42.2% with a large partial current density of 1.1 A cm−2 at −0.93 V versus the reversible hydrogen electrode. Structural characterization and in situ spectroscopic analysis reveal that the Cu‐5 quantum dots, dominated by the (100) facet, provide an abundance of active sites that enhance CO2 adsorption and activation, promoting the formation of *CO intermediates. The accumulation of *CO intermediates on the Cu active sites facilitates the CO‐CHO coupling reaction, thus enhancing the C2H4 production rate.

Unravelling the Effect of Crystal Facet of Derived-Copper Catalysts on the Electroreduction of Carbon Dioxide under Unified Mass Transport Condition.

Altering the physical structure and chemical property of copper, i.e., particle size, surface morphology, composition or crystal facet, has been demonstrated to be effective in steering the selectivity of products in electrochemical reduction of carbon dioxide. However, these modifications generally result in the change of active surface area, leading to differences in the geometric current density and local pH, which are also demonstrated to be the key factors for observed selectivity change. In this work, we deconvolute the effect of mass transport and local pH from the effect of crystal facet by investigating five copper-based catalysts with identical roughness factors for electrochemical reduction of carbon dioxide in an H-cell. Interestingly, CuO-derived catalyst stands out as the best catalyst for C-C coupling. At -1.07 V vs. RHE, the faradaic efficiency of C2+ product reaches 44.3%, with a partial current density of -10.8 mA cm-2. Electrochemical adsorption of *OH reveals that the C2+ product selectivity of derived-copper catalysts correlates positively with the ratio of Cu(100)/Cu(110) of five catalysts. Additionally, in situ Raman spectroscopy reveals that the percentage of low-frequency band linear CO (LFB-CO), which is attributed to the adsorbed *CO on Cu(100) facet, increases with the C-C coupling efficiency.

Unravelling the Effect of Crystal Facet of Derived‐Copper Catalysts on the Electroreduction of Carbon Dioxide under Unified Mass Transport Condition

Altering the physical structure and chemical property of copper, i.e., particle size, surface morphology, composition or crystal facet, has been demonstrated to be effective in steering the selectivity of products in electrochemical reduction of carbon dioxide. However, these modifications generally result in the change of active surface area, leading to differences in the geometric current density and local pH, which are also demonstrated to be the key factors for observed selectivity change. In this work, we deconvolute the effect of mass transport and local pH from the effect of crystal facet by investigating five copper‐based catalysts with identical roughness factors for electrochemical reduction of carbon dioxide in an H‐cell. Interestingly, CuO‐derived catalyst stands out as the best catalyst for C‐C coupling. At ‐1.07 V vs. RHE, the faradaic efficiency of C2+ product reaches 44.3%, with a partial current density of ‐10.8 mA cm‐2. Electrochemical adsorption of *OH reveals that the C2+ product selectivity of derived‐copper catalysts correlates positively with the ratio of Cu(100)/Cu(110) of five catalysts. Additionally, in situ Raman spectroscopy reveals that the percentage of low‐frequency band linear CO (LFB‐CO), which is attributed to the adsorbed *CO on Cu(100) facet, increases with the C‐C coupling efficiency.

Investigation of the catalytic activity of trimetallic CuAgAu aerogels for the electrochemical reduction of CO<sub>2</sub> to CO

Given the growing demand for efficient catalysts in sustainable energy applications, this study investigates the structural characterization and catalytic activity of CuAgAu trimetallic aerogels synthesized via a sol-gel method. Transmission electron microscopy (TEM) revealed a porous network structure with uniformly dispersed trimetallic nanoparticles averaging 5-10 nm in size, which indicates a successful synthesis and nanostructure formation. X-ray diffraction analysis confirmed the formation of a face-centered cubic structure, with distinct diffraction peaks observed at positions corresponding to the (111), (200), and (220) planes of Cu, Ag, and Au, respectively. These structural features are critical for understanding the crystalline nature and stability of the aerogels. The catalytic activity of CuAgAu aerogels for CO2 reduction was evaluated using linear sweep voltammetry, which showed notable enhancements in current densities at various applied potentials relative to the reversible hydrogen electrode. These findings indicate the aerogels’ effectiveness as catalysts for CO2 conversion. Furthermore, Faradaic efficiency measurements revealed a high selectivity in the conversion of CO2 to CO, achieving a high Faradaic efficiency of 85%, which suggests that the aerogels’ capability to efficiently utilize electrons in producing CO, as a valuable precursor in renewable energy and chemical synthesis applications. The combination of structural integrity, catalytic performance, and high selectivity positions CuAgAu aerogels as promising approach for sustainable energy technologies.

Mesostructure‐Specific Configuration of *CO Adsorption for Selective CO2 Electroreduction to C2+ Products

AbstractThe multi‐carbon (C2+) alcohols produced by electrochemical CO2 reduction, such as ethanol and n‐propanol, are considered as indispensable liquid energy carriers. In most C−C coupling cases, however, the concomitant gaseous C2H4 product results in the low selectivity of C2+ alcohols. Here, we report rational construction of mesostructured CuO electrocatalysts, specifically mesoporous CuO (m‐CuO) and cylindrical CuO (c‐CuO), enables selective distribution of C2+ products. The m‐CuO and c‐CuO show similar selectivity towards total C2+ products (≥76 %), but the corresponding predominant products are C2+ alcohols (55 %) and C2H4 (52 %), respectively. The ordered mesostructure not only induces the surface hydrophobicity, but selectively tailors the adsorption configuration of *CO intermediate: m‐CuO prefers bridged adsorption, whereas c‐CuO favors top adsorption as revealed by in situ spectroscopies. Computational calculations unravel that bridged *CO adsorbate is prone to deep protonation into *OCH3 intermediate, thus accelerating the coupling of *CO and *OCH3 intermediates to generate C2+ alcohols; by contrast, top *CO adsorbate is apt to undergo conventional C−C coupling process to produce C2H4. This work illustrates selective C2+ products distribution via mesostructure manipulation, and paves a new path into the design of efficient electrocatalysts with tunable adsorption configuration of key intermediates for targeted products.

Metal–Organic Frameworks for Electrocatalytic CO2 Reduction: From Catalytic Site Design to Microenvironment Modulation

AbstractThe electrochemical reduction of CO2 to high‐value carbon‐based chemicals provides a sustainable approach to achieving an artificial carbon cycle. In the decade, metal–organic frameworks (MOFs), a kind of porous crystalline porous materials featuring well‐defined structures, large surface area, high porosity, diverse components, easy tailorability, and controllable morphology, have attracted considerable research attention, serving as electrocatalysts to drive CO2 reduction. In this review, the reaction mechanisms of electrochemical CO2 reduction and the structure/component advantages of MOFs meeting the requirements of electrocatalysts for CO2 reduction are analyzed. After that, the representative progress for the precise fabrication of MOF‐based electrocatalysts for CO2 reduction, focusing on catalytic site design and microenvironment modulation, are systemically summarized. Furthermore, the emerging applications and promising research for more practical scenarios related to electrochemical CO2 conversion are specifically proposed. Finally, the remaining challenges and future outlook of MOFs for electrochemical CO2 reduction are further discussed.

Engineering a Cu-Pd Paddle-Wheel Metal-Organic Framework for Selective CO2 Electroreduction.

Optimizing the binding energy between the intermediate and the active site is a key factor for tuning catalytic product selectivity and activity in the electrochemical carbon dioxide reduction reaction. Copper active sites are known to reduce CO2 to hydrocarbons and oxygenates, but suffer from poor product selectivity due to the moderate binding energies of several of the reaction intermediates. Here, we report an ion exchange strategy to construct Cu-Pd paddle wheel dimers within Cu-based metal-organic frameworks (MOFs), [Cu3-xPdx(BTC)2] (BTC=benzentricarboxylate), without altering the overall MOF structural properties. Compared to the pristine Cu MOF ([Cu3(BTC)2], HKUST-1), the Cu-Pd MOF shifts CO2 electroreduction products from diverse chemical species to selective CO generation. In situ X-ray absorption fine structure analysis of the catalyst oxidation state and local geometry, combined with theoretical calculations, reveal that the incorporation of Pd within the Cu-Pd paddle wheel node structure of the MOF promotes adsorption of the key intermediate COOH* at the Cu site. This permits CO-selective catalytic mechanisms and thus advances our understanding of the interplay between structure and activity toward electrochemical CO2 reduction using molecular catalysts.

Concurrent activation of CO2 and H2O on sulfur-doped CNT-supported nickel phthalocyanine for electrochemical CO2 reduction to CO.

Concurrent activation of CO2 and H2O is essential for CO2 electroreduction reaction, but challenging. A sulfur-doped carbon nanotubes-supported nickel phthalocyanine (NiPc/S-CNTs) can concurrently activate CO2 and H2O, promoting CO2 protonation to *COOH. The NiPc/S-CNTs achieves CO Faraday efficiency of >96% at current density from -20 to -140 mA cm-2.

Investigating proton shuttling and electrochemical mechanisms of amines in integrated CO2 capture and utilization

Carbon capture and utilization (CCU) technologies present a promising solution for converting CO2 emissions into valuable products. Here we show how amines, such as monoethanolamine (MEA) and 2-amino-2-methyl-1-propanol (AMP), influence the electrochemical CO2 reduction process in an integrated CCU system. Using in situ spectroscopic techniques, we identify the key roles of carbamate bond strength, proton shuttling, and amine structure in dictating reaction pathways on copper (Cu) and lead (Pb) electrodes. Our findings demonstrate that on Cu electrodes, surface blockage by ammonium species impedes CO₂ reduction, whereas on Pb electrodes, proton shuttling enhances the production of hydrocarbon products. This study provides additional insights into optimizing CCU systems by tailoring the choice of amines and electrode materials, advancing the selective conversion of CO₂ into valuable chemicals.

Unconventional Electrocatalytic CO Conversion to C2 Products on Single-Atomic Pd-Agn Sites.

The electrochemical reduction of CO or CO2 into C2+ products has mostly been focused on Cu-based catalysts. Although Ag has also been predicted as a possible catalyst for the CO-to-C2+ conversion from the thermodynamic point of view, however, due to its weak CO binding strength, CO rapidly desorbs from the Ag surface rather than participates in deep reduction. In this work, we demonstrate that single-atomic Pd sites doped in Ag lattice can tune the CO adsorption behavior and promote the deep reduction of CO toward C2 products. The monodispersed Pd-Agn sites enable the CO adsorption with both Pd-atop (PdL) and Pd-Ag bridge (PdAgB) configurations, which can increase the CO coverage and reduce the C-C coupling energy barrier. Under room temperature and ambient pressure, the Pd1Ag10 alloy catalyst exhibited a total CO-to-C2 Faradaic efficiency of ~37 % at -0.83 V, with appreciable current densities and electrochemical stability, thus featuring unconventional non-Cu electrocatalytic CO-to-C2 conversion capability.

Physicochemical Analysis of Cu(II)-Driven Electrochemical CO2 Reduction and its Competition with Proton Reduction.

The reduction of CO2 has become a key role in reducing greenhouse gas emissions in efforts to search for long-term responses to climate change. We report a a couple of CO2-reducing molecular catalysts based on earth-abundant copper complexes. These are [Cu(DPA)(PyNAP)] (1) and [Cu(DPA)(PyQl)] (2) (where, DPA = pyridine-2,6-dicarboxylic acid, PyNAP = 2-(pyridin-2-yl)-1,8-naphthyridine, and PyQl = 2-(pyridin-2-yl)quinoline). The copper metal-catalysed 2-electron reduction of CO2 to CO in the presence of 2-protons is challenging. These catalysts exhibit the production of CO gas in DMF/water mixtures, achieving an impressive faradaic efficiency of 84% and 72% for complex 1 and 2 at -1.7 V vs. SCE, respectively, for selective CO2 reduction. The production of H2 due to 2H+ + 2e- was also observed as a byproduct through the competitive proton reduction reaction. This was cross-verified by online gas and mass analysis.Our investigations confirmed the stability of the electrocatalysts under the electrocatalytic conditions. The mechanistic pathways were proposed to work with the EECC and ECEC (E: electrochemical and C: chemical) mechanisms. A CO2 insertion into an in-situ generated hydride from the Cu-center generates CO through the favourable path.

Steering the Selectivity of CORR from Acetate to Ethanol via Tailoring the Thermodynamic Activity of Water

AbstractThe electrochemical conversion of carbon monoxide (CO) into oxygenated C2+ products at high rates and selectivity offers a promising approach for the two‐step conversion of carbon dioxide (CO2). However, a major drawback of the CO electrochemical reduction in alkaline electrolyte is the preference for the acetate pathway over the more valuable ethanol pathway. Recent research has shed light on the significant impact of thermodynamic water activity on the electrochemical CO2 reduction reaction pathways, but less is understood for the electrochemical reduction of CO. In this study, we investigated how the water activity at the electrified interface can be enhanced to adjust the selectivity between acetate and ethanol. We employed an ionomer modifier to lower the local concentration of alkali ions (via Donnan exclusion), successfully enhancing ethanol production while suppressing acetate formation. We observed a remarkable improvement in the Faradaic efficiency of ethanol and alcohol (i. e. ethanol, propanol etc), which reached 42.5 % and 55.1 %, respectively, at a current density of 700 mA cm−2. The partial current densities of ethanol and alcohol reached 698 and 942 mA cm−2 at 2000 mA cm−2. Furthermore, we achieved a 3.7‐fold increase in the ethanol/acetate ratio, providing clear evidence of our successful modulation of product selectivity.

Engineering single-atomic Ni sites stabilized with adjacent spinel nanoparticles to boost CO2 electroreduction

Single-atom catalysts show great potential in the electrochemical CO2 reduction reaction (CO2RR), but face significant challenges in accelerating reaction kinetics. Herein, we develop a three-dimensional heterostructured MgAl2O4/Ni-N-C catalyst via a facile pyrolysis strategy, featuring abundant atomically dispersed Ni sites and ∼14 nm MgAl2O4 nanoparticles. The MgAl2O4 with rich oxygen vacancies is crucial for stabilizing Ni atoms and promoting CO2 activation, thereby contributing to an excellent selectivity of nearly 100 % and good stability for CO production. The CO Faraday efficiency remains > 90 % within a large potential window (−0.57 to −0.97 V vs. RHE), and achieves the maximum of 98.7 % at −0.82 V. Theoretical calculations reveal that MgAl2O4 introduction can modulate the electron structure of Ni atoms, and accelerate the formation of *COOH intermediate, thus boosting CO2RR performance. This research provides a novel approach for the design of high-efficiency single-atom catalysts for CO2 conversion.

Entropy-Derived Synthesis of the CuPd Sub-1nm Alloy for CO2-to-acetate Electroreduction.

Bimetallic alloys exhibit remarkable properties in catalysis and energy storage, while their precise synthesis at the subnanoscale remains a formidable challenge due to their immiscible nature in thermodynamics. In this study, we engineer an atomically dispersed CuPd alloy with an average size of 1.5 nm loaded on CuO and phosphomolybdic acid (PMA) coassembly subnanosheets (CuO-PMA SNSs). Driven by the high vibrational entropy, Cu atoms could escape from CuO supports and bond with adjacent Pd single atoms, leading to the in situ formation of CuPd alloys. Furthermore, this strategy can also be utilized for synthesizing the ZnPt alloy with an average size of 1 nm, thereby providing a general pathway for the design of immiscible subnanoalloys. The fully exposed Cu-Pd pairs in CuPd subnanoalloys significantly enhance the adsorption and coverage of surface *CO during the electrochemical reduction of CO2, thereby leading to enhanced stability of ethenone intermediates and facilitating the production of C2 compounds. The resulting CuPd subnanoalloy exhibits a remarkable Faradaic efficiency of 46.5 ± 2.1% for CO2-to-acetate electroreduction and achieves a high acetate productivity of 99 ± 2.8 μmol cm-2 at -0.7 V versus RHE.

Harnessing in-situ oxidation of nanostructured mxene to modulate the electronic structure for improved selectivity for electrochemical carbon dioxide reduction

The electrochemical CO2 reduction reaction (CO2RR) is a promising approach to valorizing CO2. Ti3C2TX as a support material has received significant interest in enhancing CO2RR performance for tuning the electronic structure. However, there has been relatively less focus on changes to the Ti3C2TX electronic structure induced by loading catalysts onto the Ti3C2TX. Because Ti3C2TX has an intrinsic activity for both CO2RR and the competitive hydrogen evolution reaction (HER), electronic structure changes can affect the balance between CO2RR and HER selectivity. Therefore, tuning the electronic structure of Ti3C2TX can control the competition between CO2RR and HER and tune the selectivity and activity. Herein, we report that Ti3C2TX’s electronic structure can be tuned by the Ag+ loading method via redox interactions, tuning the reaction selectivity and activity for CO2RR. To illustrate this effect, we compare the CO2RR performance of in-situ formed Ag nanoparticles (NPs) on Ti3C2TX (0.9Ag-IS-Ti3C2TX) with physically mixed Ag NPs and Ti3C2TX (0.9Ag/P/Ti3C2TX). Here, ‘0.9’ refers to the molar ratio between Ag precursor and Ti3C2Tx, and ‘IS’ vs. ‘P’ refers to in-situ formed vs. physically mixed Ag NPs. 0.9Ag-IS-Ti3C2TX demonstrates a higher oxidation state for Ti and a higher proportion of Ti-O bonds than 0.9Ag/P/Ti3C2TX. Compared to 0.9Ag/P/Ti3C2TX, 0.9Ag-IS-Ti3C2TX exhibits higher CO Faradaic efficiency (FE), rising from 8.1 % with a partial current density of −2.0 mA cm−2 to 49.6 % with a partial current density of −20.1 mA cm−2 at −1.4 V vs. RHE (reversible hydrogen electrode). To harness this effect, we demonstrate control over the CO: H2 ratio of syngas formed from CO2RR over our Ti3C2TX-supported catalysts. Further electrochemical anodic oxidation experiments reveal the critical oxidation potential of Ti3C2TX (0.8 V vs. RHE) and show that HER can be partially suppressed by partial oxidation of Ti3C2TX. This work highlights the importance of considering the changes in Ti3C2TX (and other) supports when supporting catalysts for CO2RR and other electrochemical reactions.

Cascade Conversion of CO2 to Ethylene Carbonate under Ambient Conditions.

Ethylene carbonate (EC) is the simplest cyclic carbonate with great industrial significance, most importantly as the vital electrolyte component for lithium-ion batteries. Its conventional synthesis generally involves the use of toxic precursors and requires elevated temperatures and pressures. Herein, we propose a cascade catalytic route for converting CO2 to EC under ambient conditions. Such a hybrid reaction scheme consists of the electrochemical reduction of CO2 to ethylene catalyzed by copper in a membrane electrode assembly reactor, the bromine-mediated conversion of ethylene to bromoethanol catalyzed by WO3 nanoarrays grown on carbon cloth, and the reaction between bromoethanol and CO2 to form EC. By separately optimizing individual catalytic steps and then integrating them together in series, we achieved the conversion of CO2 to EC at a good yield under room temperature and atmospheric pressure. Our study also represents the first demonstration about the successful synthesis of organic carbonates from CO2 as the exclusive carbon source.

Potentiostatic electrodeposition of copper, indium, and cadmium sulfides for CO2 electroreduction: A path toward sustainable hydrogen generation

This study focuses on the potentiostatic electrodeposition of copper indium and cadmium sulfide (CuS, In2S3, and CdS) thin films on copper substrates, aiming to develop efficient electrocatalysts for the electrochemical reduction of CO2 and sustainable hydrogen generation. Utilizing Cu Kα radiation for X-ray diffraction (XRD) analysis, the crystal structures of the electrodeposited films were confirmed, revealing well-defined crystalline phases. The films exhibited average particle sizes of 55.99 nm for CuS, 50.37 nm for In2S3, and 63.51 nm for CdS. Cyclic voltammetry and chronoamperometry were employed to optimize the deposition parameters, ensuring efficient nucleation and growth of the metal sulfide films. The electrochemical performance of the synthesized electrocatalysts was rigorously tested, demonstrating their potential for CO2 reduction under optimized conditions with the highest efficiency for CdS electrodes. Additionally, the electrodeposited CuS and CdS are of the p-type, and In2S3 is of the n-type semiconductor were studied and verified by the Mott–Schottky test. CuS, In2S3, and CdS were found to have donor and acceptor concentrations (ND) of 1.68 × 106, 1.44 × 105, and 8.9 × 105 cm3, respectively. The photoelectrochemical measurements of the electrodeposited metal sulfides were studied at ambient temperature and under illumination, providing higher photocurrent responses for CdS and demonstrating its strong potential as a photoelectrode material for CO2 reduction. This work underscores the significance of facile electrochemical synthesis methods in developing cost-effective and scalable electrocatalysts, paving the way for their integration into photoelectrochemical systems for green energy applications.

A Regenerable Bi-Based Catalyst for Efficient and Stable Electrochemical CO2 Reduction to Formate at Industrial Current Densities.

Renewable electricity shows immense potential as a driving force for the carbon dioxide reduction reaction (CO2RR) in production of formate (HCOO-) at industrial current density, providing a promising path for value-added chemicals and chemical manufacturing. However, achieving high selectivity and stable production of HCOO- at industrial current density remains a challenge. Here, we present a robust Bi0.6Cu0.4 NSs catalyst capable of regenerating necessary catalytic core (Bi-O) through cyclic voltammetry (CV) treatment. Notably, at 260 mA cm-2, faradaic efficiency of HCOO- reaches an exceptional selectivity to 99.23 %, maintaining above 90 % even after 400 h, which is longest reaction time reported at the industrial current density. Furthermore, in stability test, the catalyst was constructed by CV reconstruction to achieve stable and efficient production of HCOO-. In 20 h reaction test, the catalyst has a rate of HCOO- production of 13.24 mmol m-2 s-1, a HCOO- concentration of 1.91 mol L-1, and an energy consumption of 129.80 kWh kmol-1. In situ Raman spectroscopy reveals the formation of Bi-O structure during the gradual transformation of catalyst from Bi0.6Cu0.4 NBs to Bi0.6Cu0.4 NSs. Theoretical studies highlight the pivotal role of Bi-O structure in modifying the adsorption behavior of reaction intermediates, which further reduces energy barrier for *OCHO conversion in CO2RR.