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Raw source: Strain Regulation Enhances the CO Coverage on Cu2O Surface for CO2 Electroreduction

Advanced Energy Materials

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RESEARCH ARTICLE

Strain Regulation Enhances the *CO Coverage on Cu2O Surface for CO2 Electroreduction to Ethylene Under Industrial-Level Current Density Zhiqing Yan Peng Gao Zhong Li Dong Cao Daojian Cheng

State Key Laboratory of Organic-Inorganic Composites and College of Chemical Engineering, Beijing University of Chemical Technology, Beijing, China

Correspondence: Dong Cao (caod@mail.buct.edu.cn) Daojian Cheng (chengdj@mail.buct.edu.cn)

Received: 12 August 2025 Revised: 7 November 2025 Accepted: 25 November 2025

Keywords: C─C coupling | electrochemical CO2 reduction reaction | ethylene | in situ characterization | lattice strain

ABSTRACT
Electrochemical CO2 reduction reaction (CO2 RR) to ethylene (C2 H4 ) is still a significant challenge under industrial current density.
In this study, Cu2 O with various lattice strain is prepared via an in situ reconstruction strategy. Notably, Cu2 O with 17.6% lattice
strain rate (LS17.6% Cu2 O) could achieve a Faradaic efficiency of 76.97% during CO2 RR to C2 H4 under the industrial current density
of 800 mA cm−2 . Meanwhile, the energy efficiency of the cathode cell and full cell get 43.67% and 48.69%, respectively, which are the
best values among Cu2 O catalysts. In situ attenuated total reflection surface-enhanced infrared absorption spectroscopy indicates
that the LS17.6% Cu2 O catalyst with moderate lattice strain possesses the highest surface coverage of *CO during the CO2 RR. Further
density functional theory calculations reveal the moderate lattice strain shifts the d-band center of LS17.6% Cu2 O from −2.28 to
−2.06 eV, thereby enhancing the adsorption energy of *CO and reducing the energy barrier for the dimerization of *CO to form
the *COCO intermediate. This work develops a precise strain regulation strategy to enhance the activity of CO2 electroreduction
to ethylene under the industrial conditions.

1 Introduction tion reaction (HER) and the formation of other carbonaceous by-products, significantly reduce the selectivity and faradaic Renewable electricity-driven carbon dioxide reduction reaction efficiency toward C2 H4 [9]. These critical issues will be further (CO2 RR) contributes to the achievement of carbon neutrality aggravated under the industrial-scale current density [10, 11]. and enables the production of high-value-added chemicals [1–3]. Among various products of CO2 RR, ethylene (C2 H4 ) constitutes To address the issue of low selectivity in CO2 to C2 H4 at high a critical industrial feedstock, and its selectivity determines the current densities, lattice strain engineering has emerged as a economic feasibility of the reaction [4, 5]. However, the electrocat- promising approach to modulate the electronic structure and alytic conversion of CO2 to C2 H4 remains a formidable challenge. geometric configuration of catalysts, thereby influencing the The complex reaction mechanism involves in multiple proton- adsorption and activation of reaction intermediates [12]. Wu electron transfer steps and intricate C─C coupling processes, et al. employed a redox strategy to induce strain on the surface which are often hindered by sluggish reaction kinetics [6–8]. of Cu nanocrystals. Their findings suggest that strain variations Moreover, competing reactions, such as the hydrogen evolu- influence the distribution of coordinated potassium ions on the

Zhiqing Yan and Peng Gao contributed equally to this work.

© 2025 Wiley-VCH GmbH

Advanced Energy Materials, 2026; 16:e04495 1 of 11 https://doi.org/10.1002/aenm.202504495 16146840, 2026, 5, Downloaded from https://advanced.onlinelibrary.wiley.com/doi/10.1002/aenm.202504495 by Zhejiang University Of Technology, Wiley Online Library on [16/05/2026]. See the Terms and Conditions (https://onlinelibrary.wiley.com/terms-and-conditions) on Wiley Online Library for rules of use; OA articles are governed by the applicable Creative Commons License

FIGURE 1 a) Schematic diagram of catalyst synthesis with different degrees of strain. b,c) HRTEM images of Cu2 O and LS3.7% Cu2 O. The inset at the bottom right shows a SAED graph. d) AC-TEM image of LS17.6% Cu2 O. e) HRTEM image of LS18.3% Cu2 O. f–i) Inverse FFT images of Cu2 O, LS3.7% Cu2 O, LS17.6% Cu2 O and LS18.3% Cu2 O. j) elemental mapping of LS17.6% Cu2 O.

catalyst surface, thereby altering the surface coverage of *CO the binding energies of key intermediates and promoting the intermediates [13]. From an electronic structure perspective, desired reaction pathways [15–17]. Liu et al. revealed that the lattice strain can modify the catalyst electronic density of high tensile strain from hBN epitaxial growth shifts the Cu states (DOS), thereby tuning its interaction strength with d-band center upward, strengthening *CO adsorption and reaction intermediates [14]. The d-band center of metal-based increasing surface *CO coverage, consequently lowering the catalysts can be tuned by introducing lattice strain, altering activation barrier for C─C coupling [18]. The high coverage of

2 of 11 Advanced Energy Materials, 2026 16146840, 2026, 5, Downloaded from https://advanced.onlinelibrary.wiley.com/doi/10.1002/aenm.202504495 by Zhejiang University Of Technology, Wiley Online Library on [16/05/2026]. See the Terms and Conditions (https://onlinelibrary.wiley.com/terms-and-conditions) on Wiley Online Library for rules of use; OA articles are governed by the applicable Creative Commons License intermediates ensures abundant reactive substrates for RHE), −2.37 V (vs. RHE) and −2.47 V (vs. RHE) for 10 min each. subsequent C─C coupling, significantly facilitating the coupling HRTEM images reveal that the lattice spacing of the catalysts process [19, 20]. Wang et al. demonstrated that applying remains 2.45 Å at reconstruction voltages of −2.17 V (vs. RHE) tensile strain to copper lattices enables effective regulation and −2.27 V (vs. RHE), with no morphological differences from of dipole repulsion among adsorbed CO species. Such strain pure Cu2 O (Figures S3–S6). However, when the reconstruction control promotes favorable CO accumulation on the catalytic voltages were −2.37 V (vs. RHE) and −2.47 V (vs. RHE), the lattice surface, consequently ensuring adequate reactant supply for spacings of the catalysts were 2.47 and 2.54 Å. This indicates C─C coupling [21]. Moreover, lattice strain induces structural that the lowest reconstruction voltage causing lattice strain was rearrangements of surface atoms in the catalyst, altering −2.37 V (vs. RHE). The strain rate induced at −2.37 V (vs. RHE) the geometry and spacing of active sites. Such structural is relatively small. Therefore, we ultimately selected -2.47 V (vs. modifications can optimize the adsorption configuration of RHE) as the reconstruction voltage for this system. Three cata- reaction intermediates on the catalytic surface, mitigating steric lysts with varying degrees of lattice strain were obtained through hindrance and promoting interactions between intermediates in situ reconfiguration of Cu2 O cubes at −2.47 V (vs. RHE) for [22–24]. Despite significant progress in CO2 RR research, 10, 30, and 60 min, respectively. The volume of the reconstituted most studies have been conducted under low current density catalyst gradually increases (Figures S9–S11). As illustrated in conditions, limiting the understanding of catalyst behavior at Figure 1c–e, it can be concluded that the surface roughness of the industrially relevant high current densities [25, 26]. The unique catalyst is found to gradually enhance with the increase of the mass transfer limitations and reaction dynamics at high current reconstruction time. Surface roughness has been demonstrated to densities require catalysts with optimized activity, selectivity, exert a substantial influence on two critical factors in the context and durability. Therefore, exploring the role of lattice strain in of interfacial charge transfer capability and surface migration CO2 RR to C2 H4 under industrial current density is essential kinetics. This influence is such that it effectively regulates the for the development of practical and efficient electrocatalytic yield and selectivity of products [27]. A rough surface is composed catalyst. of numerous surface depressions, which can serve as nanocavities to enrich CO2 and adsorb intermediates (such as *CO). These In this study, we prepared catalysts with different lattice strain nanocavities located on the surface serve to increase the *CO cov- levels by using an in situ reconstruction method. Experimental erage adsorbed on the electrode surface, enhance the probability results show that the faradic efficiency and partial current density of C─C coupling for adsorbed *CO, and reduce the correspond- of ethylene could attain 76.97% and 615.7 mA/cm2 , respectively, ing reaction energy barrier. And more rough electrode surface when the lattice strain rate of Cu2 O is 17.6% (LS17.6% Cu2 O). provides an augmented electrochemical active area, thus offering Meanwhile, the energy efficiency of the cathode cell and the more reaction sites [28]. The SAED images of the four catalysts full cell reach 43.67% and 48.69%, respectively, which is the demonstrate the presence of diffraction spots corresponding to preeminent catalyst among all reported Cu2 O catalysts. In situ the (111) crystal plane of Cu2 O. Therefore, we further analyzed attenuated total reflection surface-enhanced infrared absorption the lattice fringes of the Cu2 O (111) crystal plane on different spectroscopy captures the key intermediates, such as *COCO catalysts. and *COCHO. It also indicates that the LS17.6% Cu2 O catalyst with moderate lattice strain shows the highest surface coverage As shown in Figure 1f–i, clear lattice fringes were observed of *CO during CO2 RR. Density functional theory calculations with interplanar spacings of 2.45, 2.54, 2.88, and 2.90 Å. Using reveal the moderate lattice strain elevates the d-band center the interplanar spacing of the unreconstructed Cu2 O (111) plane of LS17.6% Cu2 O from −2.28 to −2.06 eV, which enhances the (2.45 Å) as a reference, the lattice strain rates were calculated by adsorption energy of *CO and further promotes the dimerization the formula ε = (d—d0 )/d0 × 100%, yielding values of 3.7%, 17.6%, of *CO to form the *COCO intermediate, thereby improving the and 18.3%. The corresponding catalysts are named LS3.7% Cu2 O, faradic efficiency of ethylene. This study pioneers a new pathway LS17.6% Cu2 O, and LS18.3% Cu2 O, where “LS” denotes lattice strain. for selective CO2 -to-ethylene conversion through precise lattice The formation of oxygen vacancies has been identified as the root strain engineering. cause of irreversible lattice expansion [29]. According to the scan- ning transmission electron microscopy energy-dispersive X-ray spectroscopy (STEM EDS) mapping, the Cu and O elements are 2 Result and Discussion uniformly distributed (Figures S12 and S13), indicating the pres- ence of O vacancies. The energy spectrum analysis of the cross 2.1 Catalyst Preparation and Characterization section of carbon paper loaded with LS17.6% Cu2 O was performed, and it was found that the O elements were concentrated on the Catalysts with different lattice strain were generated by in situ reaction surface, while most of the Cu elements were distributed reconfiguration of Cu2 O at a certain potential for different times at the bottom. Time-of-flight secondary ion mass spectrometry (Figure 1a). As observed in the transmission electron microscopy (TOF-SIMS) was employed to conduct an in-depth analysis of (TEM) images, the Cu2 O is cubic in shape around 50 nm and the catalyst’s elemental distribution. The dark black region in the Cu and O elements are uniformly distributed (Figures S1 and Figure S14a represents the sputtered pit from the TOF-SIMS depth S2). High-resolution transmission electron microscopy (HRTEM) profiling, with a maximum pit depth of 1 micrometer. Figure S14b further revealed that the surface of the Cu2 O cube was smooth reveals a high initial oxygen content, indicating a rich oxygen- and exhibited diffraction spots corresponding to the crystalline rich surface. Conversely, the initial copper content is very low, faces of Cu2 O (200) and Cu2 O (111) from the selected area electron suggesting only trace amounts of Cu exist on the sample surface. diffraction (SAED) images (Figure 1b). In situ reconstruction of We attribute this low copper content to Cu2 O. Despite increasing Cu2 O cubes were performed at −2.17 V (vs. RHE), −2.27 V (vs. depth, the Cu concentration remains negligible, confirming no

Advanced Energy Materials, 2026 3 of 11 16146840, 2026, 5, Downloaded from https://advanced.onlinelibrary.wiley.com/doi/10.1002/aenm.202504495 by Zhejiang University Of Technology, Wiley Online Library on [16/05/2026]. See the Terms and Conditions (https://onlinelibrary.wiley.com/terms-and-conditions) on Wiley Online Library for rules of use; OA articles are governed by the applicable Creative Commons License pure Cu formation occurs within the 0–1 µm depth range. LS17.6% Cu2 O revealed main peaks between Cu─O and Cu─Cu Consequently, we conclude that the oxygen vacancies formed coordination, indicating the coexistence of Cu─O and Cu─Cu by the reconfiguration were predominantly distributed on the coordination in LS17.6% Cu2 O (Figure 2h). Fitting results show electrode surface, thereby inducing lattice strain on the catalyst that the bond lengths for Cu─O and Cu─Cu are 1.85 and surface. 2.56 Å, respectively, with coordination numbers of 1 and 6 for the Cu centers in Cu─O and Cu─Cu, respectively (Table The X-ray diffraction (XRD) pattern of the Cu2 O cube exhibited S2). Additionally, we performed wavelet transforms (WTs) on a high degree of similarity to the standard card (PDF#99-0041), the Cu K-edge EXAFS spectrum, further confirming the coor- suggesting the absence of crystalline impurities. XRD analysis of dination structures of the Cu centers in Cu─O and Cu─Cu LS3.7% Cu2 O, LS17.6% Cu2 O, and LS18.3% Cu2 O indicates that during (Figure 2i). the in situ reconstruction process, a partial phase transition occurs from Cu2 O to metallic Cu0 [30]. Combined with the STEM EDS and TOF-SIMS results, the working electrode surface mainly 2.2 CO2 Electroreduction Performance consists of Cu2 O undergoing lattice strain, while metallic Cu is distributed in the deeper layers. Current research indicates The CO2 electrolysis performance of Cu2 O, LS3.7% Cu2 O, that zero-valent copper-based catalysts favor the formation of C1 LS17.6% Cu2 O, and LS18.3% Cu2 O were evaluated in membrane products, while copper-based catalysts with +1 valence promote electrode assembly (MEA) cell and flow cell using 1M KOH the generation of multicarbon products. Therefore, we conclude as the electrolyte (Figure 3a). As illustrated in Figure 3b, the that Cu2 O exposed on the surface is more conducive to the linear sweep voltammetry (LSV) curves obtained in the MEA formation of C2 products [31]. As shown in Figure 2a, all four assembly of the four samples are displayed. The LSV curves samples exhibit diffraction peaks corresponding to the Cu2 O (111) demonstrate that, compared to other catalysts, the reduction crystal plane at 36.4◦ , which is consistent with the SAED results. current density of LS17.6% Cu2 O is considerably augmented at It is noteworthy that in Figure 2b, the positions of the diffraction equivalent potentials. This phenomenon can be attributed peaks corresponding to the Cu2 O (111) crystal plane in LS3.7% Cu2 O, to the fact that moderate lattice strain optimizes the d-band LS17.6% Cu2 O, and LS18.3% Cu2 O have all shifted toward lower angles, center, thereby enhancing the selectivity of C2 products in the thereby further confirming that the reconstructed samples have CO2 reduction [39]. Excessive strain causes the center of the undergone varying degrees of lattice expansion [32]. To provide metal d band to deviate from its optimal position, resulting in direct evidence for the formation of oxygen vacancies, electron excessively high or low adsorption energy of the intermediate paramagnetic resonance (EPR) characterization was performed [40]. LS17.6% Cu2 O exhibits the highest double-layer capacitance, on different samples (Figure 2c). The results demonstrate that suggesting that a greater number of active sites on the catalyst the concentration of O vacancies increases in proportion to surface leads to improved electrocatalytic performance (Figures the prolongation of the reconstruction time. Consequently, O S19–S22). The Tafel slope of pure Cu2 O is higher than that of the vacancies were generated after in situ reconstruction at −2.47 V three reconstructed catalysts, further indicating that roughness (vs. RHE), which led to lattice strain, consistent with the HRTEM promotes electron transport during the reaction process. More characterization results. X-ray photoelectron spectroscopy (XPS) importantly, the Tafel slope of LS17.6% Cu2 O is significantly lower analysis was utilized to investigate the chemical composition and than that of other two samples, indicating that LS17.6 %Cu2 O elemental valence state of the catalyst surface. As demonstrated exhibits faster electrocatalytic reaction kinetics and charge in Figure 2d, the high-resolution Cu 2p XPS spectra of the four transfer efficiency (Figure 3c). We evaluated the catalytic samples at 932.6 eV (Cu 2p3/2) and 952.6 eV (Cu 2p1/2) correspond selectivity of gas-phase products and liquid-phase products using to Cu+ or Cu0 , respectively [33]. To further differentiate the Cu+ gas chromatography (GC) and H Nuclear Magnetic Resonance and Cu0 , Cu LMM Auger spectras were obtained (Figure 2e). Spectra (1 H NMR), respectively. The product distribution of each The binding energies of all samples are located at 570.18 eV, catalyst was measured in the flow cell under the voltage from indicating that Cu+ is the dominant species on the catalyst surface −1.2 to −2.2 V (vs. RHE). This range does not induce catalyst [34]. As illustrated in Figure 2f, the O1s XPS spectra of Cu2 O, reconstructed. The evaluation results demonstrated that the LS3.7% Cu2 O, LS17.6% Cu2 O, and LS18.3% Cu2 O are presented. The peak faradaic efficiencies (FE) of ethylene for Cu2 O, LS3.7% Cu2 O, corresponding to O vacancy (531.9 eV) is observed in all four LS17.6% Cu2 O, and LS18.3% Cu2 O were 20%, 51.1%, 76.97%, and samples, and the content of O vacancies increases with prolonged 49.64%, respectively. For Cu2 O cubes, hydrogen evolution is the reconstruction time (Table S1), which is consistent with the main side reaction (Figure S23). Additionally, the formic acid EPR characterization [35]. The characterization of the chemical produced by Cu2 O is higher than that of the other three catalysts. state and local fine structure of catalysts is performed by means However, the LS3.7% Cu2 O, LS17.6% Cu2 O, and LS18.3% Cu2 O samples of X-ray absorption spectroscopy (XAS). X-ray absorption near- that underwent lattice strain after reconstruction exhibited a edge structure (XANES) spectra demonstrates that the absorption reduced tendency to produce H2 . This observation suggests edge position of LS17.6% Cu2 O is situated between copper foil that lattice strain may play a pivotal role in diminishing the and Cu2 O, confirming its valence state to be 0–1. This finding occurrence of the hydrogen evolution reaction (HER). Despite indicates that a portion of Cu2 O is reduced to metallic Cu the relatively low HER of LS3.7% Cu2 O and LS18.3% Cu2 O, the during the reconstruction process (Figure 2g), a conclusion that substantial generation of CO results in a decline in ethylene is in alignment with the XRD result. In addition, the related selectivity, as evidenced by Figures S24 and S25. In addition shoulder peak appearing at 8982 eV proves that O vacancies to gas-phase products, LS3.7% Cu2 O and LS18.3% Cu2 O also yield caused asymmetry in the copper coordination environment, liquid-phase products including ethanol and formic acid, which which in turn induced lattice strain [36–38]. Meanwhile, the significantly reduce ethylene formation. LS17.6% Cu2 O achieved extended Cu k-edge X-ray absorption fine structure (EXAFS) of selective production of ethylene over a wide current density

4 of 11 Advanced Energy Materials, 2026 16146840, 2026, 5, Downloaded from https://advanced.onlinelibrary.wiley.com/doi/10.1002/aenm.202504495 by Zhejiang University Of Technology, Wiley Online Library on [16/05/2026]. See the Terms and Conditions (https://onlinelibrary.wiley.com/terms-and-conditions) on Wiley Online Library for rules of use; OA articles are governed by the applicable Creative Commons License FIGURE 2 a) XRD patterns and b) magnified XRD patterns of Cu2 O, LS3.7% Cu2 O, LS17.6% Cu2 O and LS18.3% Cu2 O. c) EPR spectra of four samples. High-resolution XPS spectra of d) Cu 2p, e) Cu LMM and f) O1s for four samples. g) Normalized XANES spectra of the Cu K-edge of LS17.6% Cu2 O. h) Fourier transform of Cu K-edge EXAFS spectra of LS17.6% Cu2 O. i) Wavelet transform for the Cu K-edge EXAFS spectra of LS17.6% Cu2 O.

range of 200–1000 mA/cm2 , and when the current density was results indicate that Cu undergoes severe hydrogen evolution 800 mA/cm2 , FEC2H4 reached a maximum of 76.97% (Figure 3e). reactions within the current density range of 100–1000 mA/cm2 , At the same time, the ethylene partial current density reached with ethylene Faraday efficiency peaking at only 15.45% (Figure a maximum of 615.7 mA/cm2 (Figure S26). As illustrated in S27). Furthermore, the EEC2H4 of Cu is merely 0.12 times that the product distribution diagram of LS17.6% Cu2 O, when the of LS17.6% Cu2 O (Figure S28). Based on TOF-SIMS, STEM-EDS, current density is below 1000 mA/cm2 , FEH2 can be sustained at and XRD analyses, it was concluded that the underlying Cu approximately 20%. As the current density rises, FECO exhibits a layer does not affect the material’s performance. In addition to gradual decrease, reaching less than 10% (Figure 3f). It is posited its optimal CO2 −to─C2 H4 activity and selectivity, LS17.6% Cu2 O that moderate lattice strain can adsorb *CO intermediates and also exhibits commendable stability. Stability test on LS17.6% Cu2 O undergo C─C coupling to produce ethylene. The performance of was conducted using hydrophobic carbon paper, replenishing pure copper catalysts has also been investigated. Experimental the electrolyte at 14 and 25 h to minimize concentration effect.

Advanced Energy Materials, 2026 5 of 11 16146840, 2026, 5, Downloaded from https://advanced.onlinelibrary.wiley.com/doi/10.1002/aenm.202504495 by Zhejiang University Of Technology, Wiley Online Library on [16/05/2026]. See the Terms and Conditions (https://onlinelibrary.wiley.com/terms-and-conditions) on Wiley Online Library for rules of use; OA articles are governed by the applicable Creative Commons License FIGURE 3 a) Schematic illustration of the MEA device. b) LSV curves, c) Tafel slopes and d) FEC2H4 of Cu2 O, LS3.7% Cu2 O, LS17.6% Cu2 O and LS18.3% Cu2 O. e) FEC2H4 and f) product distribution of LS17.6% Cu2 O at different current densities. g) Stability test of LS17.6% Cu2 O at 700 mA/cm2 . h) CEEC2H4 and EEC2H4 at different strain rates.

Through CO2 RR electrolysis in the flow cell at 700 mA/cm2 , nisms of CO2 RR on various catalysts in this work. In situ Raman the Faradaic efficiency of ethylene can be maintained above analysis was conducted to initiated our research on Cu2 O and 60% for 32 h (Figure 3g). Furthermore, the cathode energy LS17.6% Cu2 O from OCP to −1.3 V (vs. RHE). As demonstrated efficiency (CEE) and full cell energy efficiency (EE) of samples in Figures 4a, there is only one peak presenting at ∼450 cm−1 , with different strain rates were evaluated in the flow cell and which represents *OH [5]. The adsorbed *OH originates from the MEA cell. Figure 3h elucidates that CEE and EE manifest a electrolyte. It is remarkable that LS17.6% Cu2 O displays peaks at 350, volcanic trend as the lattice strain rate increases, with CEE and 600, and 700 cm−1 . The peaks at 350 and 600 cm−1 correspond EE attaining maximum of 43.67% and 48.69% at a lattice strain to Cu─CO stretching and oxygen vacancy, respectively [41–42]. rate of 17.6%. The peak at 600 cm−1 further corroborates the hypothesis that O vacancies were formed on the surface after in situ reconstruction of the Cu2 O cube, a conclusion that is consistent with the 2.3 Mechanistic Investigation results of the EPR and XPS characterization. Meanwhile, the peak appearing at 700 cm−1 is attributed to *COO− . The subsequent Electrochemical in situ Raman spectroscopy and in situ attenu- protonation of this intermediate can form *COOH, which serves ated total reflection surface-enhanced infrared absorption spec- as the precursor for the formation of *CO. In comparison to the troscopy (ATR-SEIRAS) were employed to elucidate the mecha- Cu2 O cube, the pronounced Cu─CO stretching peak observed

6 of 11 Advanced Energy Materials, 2026 16146840, 2026, 5, Downloaded from https://advanced.onlinelibrary.wiley.com/doi/10.1002/aenm.202504495 by Zhejiang University Of Technology, Wiley Online Library on [16/05/2026]. See the Terms and Conditions (https://onlinelibrary.wiley.com/terms-and-conditions) on Wiley Online Library for rules of use; OA articles are governed by the applicable Creative Commons License FIGURE 4 a) In situ Raman spectra of Cu2 O. b) In situ Raman spectra of LS17.6% Cu2 O. c–f) In situ ATR-SEIRAS spectra of electrochemical CO2 reduction on LS17.6% Cu2 O, ranging from −0.2 to −1.2 V (vs. RHE). The ATR-SEIRAS spectra collected at OCP is shown for comparison. g) *CO intermediates (1950 cm−1 for *CObridge , 2086 cm−1 for *COtop ) at different strain rates. h) Schematic diagram of the role of LS17.6% Cu2 O in the conversion process from CO2 to C2 H4 .

on LS17.6% Cu2 O indicates that *CO is adsorbed on Cu sites with formation of *CO (Figure 4d,e) [45]. In situ ATR-SEIRAS spectra asymmetric coordination environments, specifically the catalyst of Cu2 O, LS3.7% Cu2 O, and LS18.3% Cu2 O also showed *COOH surface with lattice strain [43, 44]. (Figures S33–S35). The ATR-SEIRAS spectrum of the LS17.6% Cu2 O catalyst exhibits multiple peaks, when initiated from −0.2 V vs. In situ ATR-SEIRAS spectroscopy was carried out to further RHE. The peaks observed at 2086 and 1950 cm−1 correspond to top monitor and identify the adsorbed intermediates under CO2 RR and bridge conformations of *CO adsorption, which has proven to conditions, providing an in-depth study of the ethylene formation be effective method for evaluating the extent of *CO coverage on mechanism (Figure 4c,d). As the applied potential increased the catalyst (Figure 4f) [46]. A superior *CO surface coverage has from OCP to −1.2 V vs. RHE, the series of spectra obtained been identified as a pivotal factor in effectively inhibiting HER for LS17.6% Cu2 O exhibited a gradual increase in the intensity of and promoting subsequent C─C coupling, thereby improving characteristic peaks, indicating the accumulation of CO2 RR inter- the conversion rate of CO2 to C2 H4 [47, 48]. In addition, the mediates. The peak at ∼1250 cm−1 is attributed to the vibration peak near 1530 cm−1 corresponds to the *COCO intermediate peak of *COOH (key intermediate), which is the precursor to the formed by *CO dimerization [49]. The *CO adsorption behavior

Advanced Energy Materials, 2026 7 of 11 16146840, 2026, 5, Downloaded from https://advanced.onlinelibrary.wiley.com/doi/10.1002/aenm.202504495 by Zhejiang University Of Technology, Wiley Online Library on [16/05/2026]. See the Terms and Conditions (https://onlinelibrary.wiley.com/terms-and-conditions) on Wiley Online Library for rules of use; OA articles are governed by the applicable Creative Commons License on LS17.6% Cu2 O and the appearance of the *COCO intermediate relative stability during the reaction process and does not undergo indicate that additional *CO adsorption can be induced at Cu additional reconstruction. sites with moderate lattice strain. This process effectively hinders *H incorporation and promotes C─C coupling, leading to the for- Based on the above analysis, the intrinsic factors in the excellent mation of the *COCO intermediate. Concurrently, a moderately performance of Cu2 O reconstructed materials induced by oxygen weak *COCHO characteristic peak (1440 cm−1 ) was identified, vacancies will be analyzed through density functional theory representing an intermediate product of *COCO hydrogenation calculations. The Cu2 O and LS17.6% Cu2 O related models were (Figure 4d) [50]. established, as shown in Figure 5a,b. First, the density of states (DOS) of Cu2 O and LS17.6% Cu2 O (Figure 5c) were calculated. The As indicated in Figure S36, an analysis was conducted for overlapping DOS peaks of the LS17.6% Cu2 O orbitals indicate a high the concentration of *COOH on catalysts with different strain level of orbital hybridization. According to the d-band center rates. As the strain rate increased, the concentration of *COOH theory, the movement of fermi levels near (away from) the d- exhibited a volcanic trend. Among the samples examined, Cu2 O band results in more (less) occupying antibonding states with cube exhibited the lowest concentration of *COOH. We believe surrounding atoms, corresponding to weaker (stronger) bonding. that catalysts without lattice strain have weak adsorption capacity Therefore, we calculated the d-band positions of Cu2 O and for *COOH, leading to the occurrence of HER. When the lattice LS17.6% Cu2 O, and found that LS17.6% Cu2 O has the best d-band value strain rate is 17.6%, the concentration of *COOH is highest, which of −2.06 eV, while the center of the d- band of Cu2 O is −2.28 eV. is conducive to the formation of *CO on LS17.6% Cu2 O. Figure 4g The results show that oxygen vacancies will cause the Cu2 O to displays that the catalyst with a strain rate of 17.6% possesses undergo reconstruction, thereby reducing the center of the d- the maximum *CO coverage, suggesting that LS17.6% Cu2 O exhibits band and further increasing the adsorption of the intermediate superior adsorption capacity for *CO, effectively hindering the *CO on the surface. The reconstruction phenomenon can be desorption of *CO to form CO and notably promoting C─C clearly seen in the EPR spectrum and AC-TEM images. In the CO2 coupling to form *COCO. Although LS3.7% Cu2 O exhibits a higher electroreduction reaction, the adsorption of *CO intermediate is a concentration of *COOH than both Cu2 O and LS18.3% Cu2 O, its key step that directly affects the reaction pathway, selectivity and strain level is insufficient to adsorb *CO intermediates, resulting catalytic efficiency. We calculated the adsorption energy of *CO in the desorption of *CO and the formation of CO product. on four types of samples, as shown in Figure 5h. With the increase Excessive lattice strain (18.3%) has been demonstrated to reduce of oxygen vacancies, the adsorption of *CO gradually intensifies the dispersion of active sites, weaken the adsorption capacity and then weakens, indicating that an appropriate oxygen vacancy of *CO intermediates, and increase CO selectivity. [51] Based can induce the adsorption of *CO. It was found that LS17.6% Cu2 O on the above analysis, the catalyst with a strain rate of 17.6% has better adsorption performance for *CO, with an adsorption (LS17.6% Cu2 O) has the highest concentration of *COCO, which energy of −1.11 eV. The differential charge and Bader charge of is then protonated to form ethylene (Figure S37). Based on in *CO adsorbed by different oxygen vacancies in Cu2 O were simul- situ infrared and in situ Raman characterization, a pathway for taneously calculated. The results show that when *CO is adsorbed the electro-reduction of CO2 to ethylene is proposed. The process on the surface of LS17.6% Cu2 O, electrons will be obtained from the begins with the hydrogenation of CO2 , forming *COOH. This Cu active site, which can optimize the adsorption intensity of is then reduced to water and *CO. Concurrently, higher *CO *CO and further facilitating C─C coupling to achieve the efficient coverage on LS17.6% Cu2 O facilitates *CO dimerization to form the conversion of the C2 H4 . Based on these results, we performed *COCO intermediate. The *COCO intermediate is hydrogenated systematic theoretical calculations on the entire CO2 reduction to form *COCHO, which undergoes a series of electron transfers process for Cu2 O and LS17.6% Cu2 O (Figure 5i). On LS17.6% Cu2 O, and hydrogenations to produce ethylene (Figure 4h). The cata- adsorbed CO2 (*CO2 ) undergoes two consecutive proton-electron lyst after the reaction was also characterized. As demonstrated transfer steps to form *CO via the *COOH intermediate. Then, the in Figure S38, the catalyst size post-reaction is approximately adjacent *CO molecules couple (*CO + *CO) to form the *COCO 100 nm, which is comparable to its size prior to the reaction. intermediate with an energy barrier of 0.56 eV, significantly lower HRTEM analysis reveals the presence of depressions on the than that of unreconstructed Cu2 O (0.85 eV). Comparing the catalyst surface after the reaction, while SAED imaging highlights product distribution diagrams for Cu2 O and LS17.6% Cu2 O, the the presence of Cu2 O (111) and Cu (200) crystal planes. The yield of the C1 products is significantly higher for Cu2 O than lattice fringe of LS17.6% Cu2 O post-reaction is measured at 2.88 Å, for LS17.6% Cu2 O. This indicates that the reconstructed LS17.6% Cu2 O suggesting that the catalyst’s structural integrity remains intact. catalyst with an appropriate amount of oxygen vacancies can Meanwhile, Figures S39–S41 reveal that the lattice spacings of the effectively reduce the formation energy of *CO dimerization Cu2 O, LS3.7% Cu2 O, and LS18.3% Cu2 O catalysts after reaction were into the *COCO intermediate, thereby enabling the subsequent 2.45, 2.54, and 2.90 Å, respectively. Moreover, the concentration proton-electron transfer step to form the *COCHO intermediate. trends of oxygen vacancies in all four catalysts after reaction Subsequently, the reaction pathways for CO2 conversion to remained consistent with those before reaction, indicating that ethanol and ethylene on Cu2 O and LS17.6% Cu2 O were simulated. the catalysts remained unchanged during the reaction process Starting from the *COCHO branch, hydrogenation-dehydration (Figure S42). The XRD pattern of the catalyst after the reaction yields *CHOCHO (ethylene pathway) or Cu─C bond breaks to exhibited the diffraction peak corresponding to the Cu2 O(111) produce *CH2 CHOH (ethanol pathway). For LS17.6% Cu2 O, the crystal plane at 36.4◦ . As illustrated in Figure S43, the Cu free energy of *CHOCHO is lower than that of *CH2 CHOH, in LS17.6% Cu2 O after the reaction predominantly exists in the and all subsequent hydrogenation steps are exothermic until the + form of Cu , with a significant number of O vacancies being formation of *CH2 CH2 . These results suggest LS17.6% Cu2 O has preserved. These results demonstrate that LS17.6% Cu2 O exhibits the potential to enhance the C─C coupling pathway, thereby

8 of 11 Advanced Energy Materials, 2026 16146840, 2026, 5, Downloaded from https://advanced.onlinelibrary.wiley.com/doi/10.1002/aenm.202504495 by Zhejiang University Of Technology, Wiley Online Library on [16/05/2026]. See the Terms and Conditions (https://onlinelibrary.wiley.com/terms-and-conditions) on Wiley Online Library for rules of use; OA articles are governed by the applicable Creative Commons License FIGURE 5 Models of the a) Cu2 O and b) LS17.6% Cu2 O. c) DOS of Cu2 O and LS17.6% Cu2 O. Charge difference map of *CO on the d) Cu2 O, e) LS3.7% Cu2 O, f) LS17.6% Cu2 O and g) LS18.3% Cu2 O. h) Adsorption energy of *CO on four types of samples. i) The reaction energy diagram for CO2 to C2 H4 and C2 H5 OH on Cu2 O and LS17.6% Cu2 O.

reducing the energy barrier of key steps and improving the yield are the best values among Cu2 O catalysts. In situ attenuated total and selectivity of C2 H4 . reflection surface-enhanced infrared absorption spectroscopy discloses a volcanic relationship between the lattice strain rate and surface coverage of *CO. The LS17.6% Cu2 O with moderate 3 Conclusion lattice strain shows the highest surface coverage of *CO dur- ing the CO2 RR. Further density functional theory calculations In summary, this study successfully prepared various Cu2 O demonstrate that the moderate lattice strain raises the d-band catalysts with different lattice strain by using an in situ recon- center of LS17.6% Cu2 O from −2.28 to −2.06 eV. This elevation struction method. The experimental findings confirm the faradic serves to enhance the adsorption energy of *CO, which in efficiency and partial current density of ethylene for LS17.6% Cu2 O turn facilitates the dimerization of *CO to form the *COCO are 76.97% and 615.7 mA/cm2 , respectively. Meanwhile, the energy intermediate, ultimately leading to an improvement in faradic efficiency of the cathode cell and the full cell of LS17.6% Cu2 O for efficiency for ethylene. This study provides a foundation for the ethylene correspond to 43.67% and 48.69%, respectively, which rational design of high-performance noble metal free catalysts,

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