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. 2026 Jun 10;65(33):e2590405. doi: 10.1002/anie.2590405

Atomic Coordination Engineering of MOF Nanostructures for CO2 Electroreduction to High‐Value Multi‐Carbon Products at Industrial‐Level Current Density

Juan Wang 1,2, Nana Yan 3, Lutong Shan 4, Jia Lyu 5, Qingbo Wa 1, Liang Guo 1, Fengkun Hao 1, Fu Liu 1, Mingzheng Shao 1,2, Yunhao Wang 1,2, Guozhi Wang 1, Xiang Meng 1,2, Chaohui Wang 1, Chenliang Ye 6, Yanwei Lum 7, Shibo Xi 8, Daliang Zhang 5, Peng Guo 3,9,✉, Zhanxi Fan 1,2,10,11,✉
PMCID: PMC13452521  PMID: 42272200

ABSTRACT

Metal–organic frameworks (MOFs) have shown great promise for electrochemical carbon dioxide (CO2) reduction into value‐added chemicals/fuels, thereby supporting the balance of carbon‐neutral energy cycle. The multi‐carbon (C2+) production on MOF electrocatalysts is of great significance but remains challenging due to inefficient C–C coupling. Here, we report the atomic coordination regulation of MOF nanostructures (Cu‐Trz‐Br) for efficient CO2 electroreduction by rationally designing dual‐site Cu catalysts. The crystallographic structure of Cu‐Trz‐Br is determined by three‐dimensional electron diffraction and Rietveld refinement against high‐resolution powder X‐ray diffraction data, which feature unique mixed coordination modes of Cu–N4Br2 and Cu–N4 sites. In CO2 electroreduction, Cu‐Trz‐Br demonstrates much enhanced selectivity toward C2+ products compared to common counterparts with only Cu–N4 sites, enabling efficient C2+ production under industrial‐level current density. In situ studies and theoretical calculations reveal that the coordination regulation of Cu–N4Br2 sites promotes CO2 adsorption and activation, as well as effectively enhances local *CO availability near Cu‐Trz‐Br, thereby facilitating C–C coupling toward C2+ products.

Keywords: atomic coordination regulation, carbon dioxide reduction reaction, electrocatalysis, metal–organic frameworks, multi‐carbon products

High‐purity Cu‐MOF (Cu‐Trz‐Br) nanosheets are controllably synthesized, and the crystallographic structure is determined by three‐dimensional electron diffraction. The unconventional mixed coordination geometry of Cu–N4Br2 and Cu–N4 sites in Cu‐Trz‐Br enables the efficient C2+ production under industrial‐level current density by benefiting considerable *CO‐generating capacity and facilitating the C–C coupling process.

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1. Introduction

The renewable energy‐powered electrochemical carbon dioxide reduction reaction (CO2RR) can convert CO2 into valuable chemicals and fuels, providing a promising approach to realize sustainable carbon cycle [1, 2, 3, 4, 5, 6, 7]. Due to the appropriate binding energies of key intermediates for C–C coupling, copper (Cu)‐based electrocatalysts are particularly effective in transforming CO2 into deeply reduced multi‐carbon (C2+) products [8, 9, 10, 11]. During the C2+ formation pathway, CO2 is initially adsorbed on Cu active sites, followed by the generation of the key *CO intermediate, which is further converted into C2+ products through the rate‐determining step of the C–C coupling [12, 13, 14, 15]. Studies have found that systematically enhancing the surface coverage of *CO and lowering the energy barrier for *CO protonation into *CHO/*COH, could effectively facilitate the asymmetric C–C coupling process [16, 17, 18]. At the same time, a suitable distance between neighboring Cu active sites is of equal importance, which enables efficient dimerization of *CO and/or the adsorbed *CHO intermediate on adjacent Cu site [19, 20, 21, 22]. However, due to the sluggish kinetics of the multi‐electron transfer step and relatively high energy barriers of C–C coupling [23, 24, 25, 26], the low activity and inferior selectivity for C2+ production of most electrocatalysts still restrict the practical application of CO2RR.

With the recent significant progress in reticular chemistry, metal–organic frameworks (MOFs), especially Cu‐MOFs, have emerged as promising candidates for electrochemical CO2RR [27, 28, 29, 30]. Typically, the high surface area and tunable pore size characteristics of Cu‐MOFs could promote CO2 molecular adsorption/activation, facilitating electrochemical CO2RR [31, 32, 33]. In the meantime, the homogeneously dispersed Cu ions/clusters in MOFs provide abundant accessible active sites for electrocatalysis, which aid in exploring structure–performance relationships at the atomic level [34, 35, 36]. Recently, some MOF electrocatalysts with Cu–N4 active sites have been applied in converting CO2 toward C2+ products [19, 20, 37, 38]. However, most reported MOF electrocatalysts with isolated Cu–N4 sites still suffer from inefficient C–C coupling, primarily due to inadequate *CO coverage and/or unfavorable spatial distance of adjacent Cu sites [39, 40]. Therefore, by taking advantage of flexible structural design in Cu‐MOFs [33, 41, 42, 43], the rational coordination engineering of Cu–N4 sites shows particular promise in boosting C–C coupling, as well as gaining deep mechanistic understanding to guide catalyst design.

Herein, we report the atomic coordination engineering of Cu–N4 sites in MOF nanostructures for highly efficient CO2 electroreduction into C2+ products. High‐purity Cu‐MOF (Cu‐Trz‐Br) nanosheets are synthesized through a facile one‐pot hydrothermal method, and the crystallographic structure is systematically characterized by three‐dimensional electron diffraction (3D ED) and Rietveld refinement against high‐resolution powder X‐ray diffraction (PXRD) data. Cu‐Trz‐Br possesses a 3D framework with unique dual Cu coordination configurations of Cu–N4Br2 and Cu–N4 sites. In electrochemical CO2RR, Cu‐Trz‐Br demonstrates greatly enhanced selectivity toward C2H4 and C2+ products, compared to Cu‐Trz and CuPc with only Cu–Nx sites. It is noteworthy that Cu‐Trz‐Br also exhibits excellent selectivity for C2H4 and C2+ products under industrial‐level current density. In situ characterizations and theoretical calculations suggest that Cu–N4Br2 sites can afford a *CO‐enriched local environment and synergistically promote C–C coupling toward C2+ production.

2. Results and Discussion

2.1. Synthesis and Structural Analysis

As shown in Figure 1a, Cu‐Trz‐Br nanosheets were synthesized through a solvothermal method using cuprous bromide (CuBr) as metal precursor and 1H,1,2,4‐triazole (HTrz) as organic linker (please see “Methods” for more details). However, the nano‐sized crystals of Cu‐Trz‐Br are inaccessible to single crystal X‐ray diffraction to elucidate the atomic structure, which requires sufficiently larger (>5 µm) and well‐ordered crystals [44, 45]. Although PXRD is commonly employed for determining the structure of polycrystalline materials, the peak overlapping still restricts the precise peak indexing and intensity extraction, particularly for MOFs featuring large unit cells. The PXRD offers data averaging of millions of crystals, posing challenges in interpreting samples with multiple phases or structural variations [46, 47, 48]. Benefiting from the strong interaction between electrons and matter, 3D ED has been developed as an efficient technique for ab initio structural analysis of single crystal even with the size down to nanometers [49, 50, 51, 52]. Specially, the updated continuous rotation electron diffraction (cRED) technique realizes the quick data collection time of 3–5 min per crystal, which enables the high‐throughput analysis of individual crystals [53, 54].

FIGURE 1.

FIGURE 1

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Synthesis and structural characterization of Cu‐Trz‐Br nanosheets. (a) Schematic illustration for the synthesis of Cu‐Trz‐Br. HTrz, 1H,1,2,4‐triazole. (b) 3D reciprocal lattices of Cu‐Trz‐Br nanostructure (hkl corresponds to reciprocal space indices). (c–e) h0l (c), hk0 (d), and 0kl (e) slices cut from the 3D reciprocal lattice. (f–h) Crystallographic structures of Cu‐Trz‐Br: (f) the coordination mode of Trz– ligand; (g) coordination environment of three kinds of Cu centers; (h) the framework structure of Cu‐Trz‐Br viewed along c axis. Hydrogen atoms are omitted for clearance.

In terms of the crystallographic structure determination of Cu‐Trz‐Br, one high‐quality dataset was collected from an individual nanosheet within 3 min, and the reconstructed 3D reciprocal lattices of Cu‐Trz‐Br are illustrated in Figure 1b. The monoclinic unit cell parameters could be deduced from this dataset, and potential space groups (P2, Pm, or P2/m) could be identified based on the reflection conditions shown in Figure 1c–e. The intensity of all reflections was extracted using X‐ray Detector Software (XDS) [55]. The initial structural model was solved using the direct method in SHELXT [56], with the space group being P2/m, as well as the unit cell parameters of a = 7.1 Å, b = 9.0 Å, c = 8.0 Å, 𝛼 = 90°, 𝛽 = 116.3°, and 𝛾 = 90° (Table S1). As shown in Figure 1f,g, three kinds of Cu centers can be observed, and each Trz– ligand is coordinated with three different Cu atoms. Specifically, Cu1 and Cu2 are both hexa‐coordinated with Cu–N4Br2 sites, and Cu3 is four‐coordinated with Cu–N4 coordination configuration. For every Trz– ligand, two of three N atoms coordinate with Cu1 and Cu2 to form layered substructures, and the third N atom is connected with the Cu3 site, expanding into a 3D framework structure (Figures 1h, S1, and S2).

2.2. X‐Ray Spectral Analysis

The X‐ray photoelectron spectroscopy (XPS) was applied to study the valence state of Cu centers in Cu‐Trz‐Br (Figures 2a and S3). As shown in Figure 2a, two major peaks at 954.1 and 934.2 eV for Cu 2p3/2 and Cu 2p1/2 can be assigned to Cu(II), respectively. The other two shoulder peaks (i.e., Cu 2p3/2 (951.5 eV) and Cu 2p1/2 (931.8 eV)) are associated with Cu(I), suggesting the mixed valence states of Cu in Cu‐Trz‐Br. According to the relatively integrated peak areas, the ratio of Cu(II) to Cu(I) is calculated to be about 3 to 1, indicating that the Cu‐Trz‐Br framework features positive charges. Meanwhile, zeta potential analysis also confirms the cationic nature of the Cu‐Trz‐Br framework (Figure S4). Based on the initial structural model from 3D ED data, the crystallographic structure of Cu‐Trz‐Br was finalized by Rietveld refinement against high‐resolution PXRD results with R factor (R wp) of 6.98% (Figure 2b, Tables S2 and S3). It was found that the occupancy of coordinated Br atoms is 0.28, as well as 0.68 Br– per unit cell is distributed in the channel, balancing the positive charges from the framework. Moreover, the atomic ratio of Cu to Br is well consistent with the energy dispersive X‐ray spectroscopy (EDS) result (Figure S5). As shown in the Fourier‐transform infrared (FTIR) spectra (Figure S6), Cu‐Trz‐Br exhibits the characteristic peaks at 1629 cm−1 (C = N vibration) and 1510 cm−1 (N = N vibration), which are lower than those of the HTrz ligand, confirming the coordination mode of HTrz ligand. As shown in Figure S7, the thermogravimetric analysis (TGA) profile shows a weight loss before 100°C, which could be assigned to the removal of adsorbed water within the framework. The subsequent significant weight loss at around 300°C is attributed to the decomposition of the framework of Cu‐Trz‐Br. Meanwhile, the PXRD patterns of Cu‐Trz‐Br after soaking in 0.1 M KHCO3 or 1.0 M KOH for 24 h still align well with its simulated pattern (Figure S8), suggesting the good chemical stability in the commonly used electrolytes.

FIGURE 2.

FIGURE 2

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X‐ray structural characterizations of Cu‐Trz‐Br nanosheets. (a) XPS spectrum of Cu 2p for Cu‐Trz‐Br. (b) Rietveld refinement of the as‐synthesized Cu‐Trz‐Br was performed using Cu Kα1 radiation (λ = 1.5406 Å). The experimental, calculated, and difference profiles are shown in blue, red, and black, respectively. (c, d) Normalized XANES spectra of Cu K‐edge (c) and Fourier transform of Cu K‐edge EXAFS spectra (d) of Cu‐Trz‐Br, CuPc, CuBr and Cu foil. (e) R space fitting results of Cu K‐edge for Cu‐Trz‐Br. (f) Wavelet transform for the k2‐weighted Cu K‐edge EXAFS spectra of Cu‐Trz‐Br and Cu foil, respectively.

The X‐ray absorption near‐edge structure (XANES) and extended X‐ray absorption fine structure (EXAFS) spectroscopies were combined to investigate the electronic structure and coordination environment of Cu centers in Cu‐Trz‐Br, together with Cu phthalocyanine (CuPc), CuBr, and Cu foil as reference samples (Figure 2c–f). As shown in Figure 2c, Cu in Cu‐Trz‐Br exhibits absorption edge position between that of CuBr and CuPc, especially near that of CuPc, suggesting the mixed valence states of Cu in Cu‐Trz‐Br, which is consistent with XPS results. Meanwhile, the Fourier‐transformed Cu K‐edge EXAFS of Cu‐Trz‐Br demonstrates a similar pattern to that of CuPc with little difference, indicating the dominant Cu–N coordination in Cu‐Trz‐Br (Figure 2d). The fitting results reveal the contribution of both Cu–N and Cu–Br scattering paths in Cu‐Trz‐Br (Figure 2e and Table S4), in which the coordination number of Cu centers and the bond lengths of Cu–N and Cu–Br are well consistent with the crystallographic structure of Cu‐Trz‐Br. The wavelet transforms of Cu‐Trz‐Br feature the intensity maxima different from that of Cu foil, confirming the non‐metallic Cu state in Cu‐Trz‐Br (Figures 2f and S9).

In terms of the morphology of as‐synthesized Cu‐Trz‐Br, scanning electron microscope (SEM) and transmission electron microscope (TEM) images show that high‐purity nanosheets with a length, width, and thickness of 3.8–12.4 µm, 0.5–1.1 µm, and 170–300 nm have been synthesized (Figures 3a–c and S10). The selected‐area electron diffraction (SAED) pattern of a representative nanosheet exhibits sharp diffraction spots, which are consistent with the [001] orientation of Cu‐Trz‐Br, suggesting the single‐crystalline structure of individual Cu‐Trz‐Br nanosheet (Figure 3d,e). The low‐dose high‐resolution TEM (HRTEM) image of a representative nanosheet and the fast Fourier transform (FFT) pattern of the selected area also indicate the single‐crystalline feature and [001] orientation of Cu‐Trz‐Br nanosheets (Figure 3f,g). As shown in the zoom‐in HRTEM image (Figure 3h), an interplanar spacing of 5.21 Å for the nanosheet is assigned to the (110) plane of Cu‐Trz‐Br. Furthermore, the typical high‐angle annular dark‐field scanning TEM (HAADF‐STEM) image of a single Cu‐Trz‐Br nanosheet and corresponding EDS elemental mappings identify the homogeneous distribution of Cu, Br, N, and C elements (Figure 3i–m).

FIGURE 3.

FIGURE 3

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Microstructural characterizations of Cu‐Trz‐Br nanosheets. (a, b) Low magnification (a) and high magnification (b) SEM images of Cu‐Trz‐Br nanosheets. (c) Low magnification TEM image of Cu‐Trz‐Br nanosheets. (d, e) High magnification TEM image (d) and corresponding SAED pattern (e) of a single Cu‐Trz‐Br nanosheet. (f) A low‐dose HRTEM image of Cu‐Trz‐Br nanosheets. (g) The FFT pattern of corresponding region marked in (f). (h) Zoom‐in HRTEM image of the corresponding region marked in (e), along with the chemical structure of Cu‐Trz‐Br viewed along c axis. (i–l) HAADF‐STEM image (i) and the corresponding EDS elemental mappings (j–m) of a representative Cu‐Trz‐Br nanosheet.

2.3. Electrocatalytic CO2RR Performance Evaluation

As a proof‐of‐concept application, the as‐synthesized Cu‐Trz‐Br was applied as catalysts for CO2 electroreduction. To investigate the effect of coordination environment regulation of Cu–N4 active sites on electrochemical CO2RR, another Trz‐constructed Cu‐MOF without Br‐coordination (denoted as Cu‐Trz, Figures S11 and S12) and CuPc were selected as control samples. The electrocatalytic CO2RR test of three samples was first conducted in a gas‐tight H‐type cell with 0.1 M KHCO3 as the electrolyte. The linear sweep voltammetry (LSV) profiles (Figure 4a) show that Cu‐Trz‐Br demonstrates a much higher current density than Cu‐Trz or CuPc, suggesting the potentially higher electrocatalytic activity of Cu‐Trz‐Br. As shown in Figures 4b and S13, Cu‐Trz‐Br and Cu‐Trz demonstrate similar electrochemical CO2RR product distribution, exhibit relatively high selectivity for CO and formate at low overpotentials, and deliver enhanced selectivity toward C2+ products as the applied potential increases. In contrast, CuPc mainly promotes hydrogen evolution reaction (HER) rather than CO2RR (Figures S14 and S15).

FIGURE 4.

FIGURE 4

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Electrocatalytic CO2RR performance. (a–e) Electrocatalytic performance of Cu‐Trz‐Br, Cu‐Trz, and CuPc toward CO2RR in H‐type cell: (a) LSV curves in CO2‐saturated 0.1 M KHCO3 electrolyte; (b) the CO2RR product distributions of Cu‐Trz‐Br at different potentials; (c) the FE of C2H4 and other C2+ products at different potentials; (d) the partial current densities of C2H4 and C2+ products at different potentials; (e) the catalytic stability test of Cu‐Trz‐Br at –1.2 V (vs. RHE) for 12 h. (f, g) Electrocatalytic performance of Cu‐Trz‐Br toward CO2RR in flow cell: (f) the CO2RR product distributions of Cu‐Trz‐Br under different current densities; (g) the FE of C2H4 and other C2+ products, and partial current densities of C2+ products on Cu‐Trz‐Br under different current densities. (h) Comparison of CO2RR performance of Cu‐Trz‐Br with reported Cu‐MOFs/coordination complexes electrocatalysts.

Among various kinds of products, Cu‐Trz‐Br demonstrates impressive selectivity toward the gaseous product of C2H4 (Figure 4c). In particular, Cu‐Trz‐Br delivers much higher selectivity than Cu‐Trz and CuPc in almost the whole operating potential window. Remarkably, Cu‐Trz‐Br shows excellent FEC2H4 of 56.0% at –1.2 V (vs. RHE), much larger than the maximum FEC2H4 of 45.9% for Cu‐Trz and 7.3% for CuPc. Besides C2H4, Cu‐Trz‐Br also exhibits good catalytic selectivity toward other kinds of C2+ products, such as ethanol (C2H5OH), acetic acid (CH3COOH), and n‐propanol (n‐C3H7OH). As shown in Figure 4c, Cu‐Trz‐Br demonstrates significantly improved selectivity for C2+ production, in comparison with Cu‐Trz and CuPc. Importantly, Cu‐Trz‐Br delivers an FEC2+ of over 70% at a wide potential range and achieves the highest FEC2+ of 79.4% at –1.2 V (vs. RHE). Correspondingly, Cu‐Trz‐Br exhibits obviously enhanced partial current densities for both C2H4 and C2+ products, almost over two times or 20 times that of Cu‐Trz or CuPc in the whole potential range, respectively (Figure 4d). Moreover, Cu‐Trz‐Br also delivers higher C2+/C1 product ratios than those on Cu‐Trz or CuPc in almost the whole applied potential window, indicating the highly efficient C–C coupling on Cu‐Trz‐Br (Figure S16). Electrochemical impedance spectroscopy (EIS) was utilized to study the charge transfer characteristics (Figure S17). The fitting results revealed that Cu‐Trz‐Br exhibits the lowest charge transfer resistance (R ct) of 47.33 Ω compared to Cu‐Trz (62.17 Ω) and CuPc (89.55 Ω), suggesting the fastest charge transfer of Cu‐Trz‐Br. As shown in Figures S18–S20, electrochemical double‐layer capacitances were assessed to investigate the electrochemical active surface area (ECSA). It was found that Cu‐Trz‐Br and Cu‐Trz demonstrate a comparable C dl value, higher than that of CuPc, indicating that the Trz‐constructed Cu‐MOFs possess more active sites for electrocatalysis.

Furthermore, the long‐term CO2RR electrocatalytic stability of Cu‐Trz‐Br was investigated at –1.2 V (vs. RHE). As shown in Figure 4e, the total current density remains relatively constant, with only a slight increase over entire 12 h of electrolysis. Meanwhile, Cu‐Trz‐Br delivers excellent selectivity for C2H4 production, achieving the highest FEC2H4 of 59.7% and maintaining a high FEC2H4 of over 50.7% during the durability test. Furthermore, the selectivities toward CH4, CO, and H2 products on Cu‐Trz‐Br also remain relatively stable throughout this process. After the stability test, SEM, XPS, and PXRD (Figures S21–S23) characterizations confirm that the morphology and structure of Cu‐Trz‐Br are well preserved, indicating the good catalytic stability of Cu‐Trz‐Br for CO2RR.

To explore its potential for practical application, the electrochemical CO2RR on Cu‐Trz‐Br was also investigated in flow cell under industrial‐level current densities. As shown in Figure 4f, Cu‐Trz‐Br exhibits similar CO2RR product distribution to that in H‐type cell. Importantly, Cu‐Trz‐Br delivers superior selectivity toward C2H4 and C2+ products in a wide current density range of 250 to 500 mA cm−2 (Figures 4f and S24). The Cu‐Trz‐Br achieves the highest FEC2H4 of 51.2%, FEC2+ of 70.4%, and j C2+ of 176 mA cm−2 at around –1.27 V (vs. RHE), as well as maintains relatively good selectivity with current density up to 500 mA cm−2. It is worth noting that the electrocatalytic CO2RR on Cu‐Trz‐Br well outperforms most reported pristine Cu‐MOF/complex electrocatalysts in both neutral and alkaline electrolytes (Figures 4h and S25, Table S5).

2.4. In Situ Mechanism Study

To gain a thorough understanding of the enhanced generation of C2+ products on Cu‐Trz‐Br, in situ attenuated total reflectance Fourier‐transform infrared (ATR‐FTIR) spectroscopy was applied to track the adsorbed key intermediates during electrocatalytic CO2RR. The in situ ATR‐FTIR spectra of Cu‐Trz‐Br, Cu‐Trz, and CuPc were recorded at various applied potentials ranging from –0.05 to –1.30 V (vs. RHE) in a CO2‐saturated 0.1 M KHCO3 aqueous solution (Figures 5a, S26, and S27). Compared with CuPc, absorption peaks of C2‐related intermediates on Cu‐Trz‐Br are much more obvious, confirming the favorable generation of C2+ products. As shown in Figure 5a, absorption peaks at ∼ 1392 and ∼ 1253 cm−1 could be assigned to the symmetric vibration and C–O stretch of the *COOH intermediate, respectively [57]. The absorption peaks at 2028 and 1037 cm−1 correspond to the atop configuration of *CO adsorption and the nonplanar vibration (O = C–H) of *CHO intermediate, respectively [58]. Moreover, C2‐related intermediates could be identified as well. Obvious absorption peaks at ∼ 1515 and ∼ 1180 cm−1 are attributed to the *OCCOH intermediate [41, 59], well consistent with the asymmetric C–C coupling process for C2+ production on Cu‐Trz‐Br. Similar absorption peaks are presented in the in situ ATR‐FTIR spectra of Cu‐Trz, suggesting similar electrocatalytic CO2RR reaction pathway on Cu‐Trz. Note that the emergence of *COatop band begins at –0.35 V (vs. RHE) on Cu‐Trz‐Br, which is almost 200 and 300 mV more positive compared to Cu‐Trz and CuPc, respectively. These results indicate that the coordination configuration regulation of the Cu–N4 site in Cu‐Trz‐Br can significantly decrease the energy barrier of *CO formation, thereby enhancing the following asymmetric C–C coupling toward C2+ production [12, 26].

FIGURE 5.

FIGURE 5

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In situ characterizations of electrocatalytic CO2RR. (a) In situ ATR‐FTIR spectra of electrochemical CO2 reduction on Cu‐Trz‐Br, ranging from –0.05 to –1.30 V (vs. RHE) at an interval of 50 mV. The ATR‐FTIR spectra collected at OCP is shown for comparison. (b) In situ Raman spectra of Cu‐Trz‐Br under OCP and electrocatalytic CO2RR at different potentials. (c) In situ DEMS pattens of Cu‐Trz‐Br for electrocatalytic CO2RR. (d, e) In situ DEMS patterns of CO (d) and C2H4 (e) on Cu‐Trz‐Br, Cu‐Trz, and CuPc, respectively.

In situ Raman spectroscopy was utilized to investigate the electrocatalytic stability of Cu‐Trz‐Br (Figure 5b). Specifically, Raman spectra were acquired within the potential range of –1.0 to –1.4 V (vs. RHE) in CO2‐saturated 0.1 M KHCO3 aqueous solution. As the applied potential increases, Cu‐Trz‐Br exhibits similar Raman shift peaks to those observed at the open‐circuit potential (OCP), without noticeable shift in their inherent Raman peaks [60, 61]. Additionally, no extra or novel peaks associated with cuprous oxide or copper oxide are detected at different applied potentials [62, 63]. These results indicate that Cu‐Trz‐Br maintains relatively good stability throughout the electrocatalytic CO2RR process [41].

In situ differential electrochemical mass spectrometry (DEMS) was used to investigate the dynamic evolution process of electrocatalytic CO2RR (Figures 5c, S28, and S29). The DEMS patterns were collected by linearly sweeping the potential from –0.6 to –1.2 V (vs. RHE) at 5 mV s−1. As shown in Figure 5c, multiple characteristic mass‐to‐charge ratios (m/z) can be identified, which correspond to H2, CH4, C2H4, CO, HCOO–, and C2H5OH, respectively. As shown in Figure 5d, Cu‐Trz‐Br demonstrates a much stronger signal associated with *CO/CO species, suggesting the higher local *CO/CO concentration near Cu‐Trz‐Br electrode. Meanwhile, the characteristic *CO/CO signal on Cu‐Trz‐Br emerges around 90 or 140 s earlier than that on Cu‐Trz or CuPc, respectively [64, 65]. These results indicate that the coordination environment engineering of Cu‐Trz‐Br reduces the overpotential required for *CO/CO formation, which is the crucial source/intermediate in C–C coupling process [66]. Furthermore, typical signal for C2H4 on Cu‐Trz‐Br is observed to appear noticeably earlier than Cu‐Trz or CuPc by approximately 40 or 70 s, respectively, suggesting more favorable generation of C2H4 (Figure 5e).

2.5. Theoretical Mechanism Investigation

To gain a deeper insight into the impact of Cu coordination geometry regulation, density functional theory (DFT) calculations were conducted to explore the underlying mechanism of electrocatalytic CO2RR over Cu‐Trz‐Br and CuPc. For electrostatic potential distribution (Figure 6a, S30, and S31), it was found that the Cu centers in Cu‐Trz‐Br demonstrate higher electrostatic potential than that in CuPc, facilitating the capture and/or activation of CO2 molecules during electrocatalytic CO2RR. Meanwhile, charge density difference analysis was also performed to investigate CO2 adsorption on Cu‐Trz‐Br and CuPc. As shown in Figure 6b, Cu‐Trz‐Br exhibits stronger interaction with CO2 molecules than CuPc and shows lower CO2 adsorption energy compared to that on CuPc (Figures S32 and S33). These results further confirm that the coexistence of Cu–N4Br2 and Cu–N4 sites enables the superior CO2 binding and activation capability of Cu‐Trz‐Br. Density of states (DOS) has been calculated to clarify the orbital contributions toward electronic structures (Figure 6c,d). In comparison with CuPc, the N‐2p and Br‐2p orbitals in Cu‐Trz‐Br contribute to the p‐d hybridization, enabling the efficient electron transfer. With the changes in coordination configuration, the Cu‐3d orbitals in Cu‐Trz‐Br deliver a peak at E V=4.61 eV toward the Fermi level (E F), compared to E V=5.03 eV in CuPc. The upshift of Cu‐3d orbitals in Cu‐Trz‐Br suggests enhanced electroactivity toward CO2RR.

FIGURE 6.

FIGURE 6

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Theoretical calculations of electrochemical CO2RR on Cu‐Trz‐Br and CuPc. (a) Electrostatic potential distribution of Cu‐Trz‐Br (i) and CuPc (ii). (b) The CO2 adsorption energy on Cu‐Trz‐Br and CuPc. Insets: the corresponding charge density difference of CO2 on Cu‐Trz‐Br and CuPc. (c, d) Density of states of Cu‐Trz‐Br (c) and CuPc (d). (e) Gibbs free energy of electrochemical CO2RR toward C2+ pathways over Cu‐Trz‐Br and CuPc. (f) Gibbs free energy of hydrogen evolution reaction pathways over Cu‐Trz‐Br and CuPc.

According to in situ ATR‐FTIR and DEMS results, it was found that Cu coordination configuration regulation in Cu‐Trz‐Br could effectively promote CO/*CO formation, which are widely known as key intermediates for C–C coupling process [20, 67, 68]. Therefore, the energy barrier for converting CO2 to *CO was calculated over Br‐coordinated Cu1/Cu2 and Cu3 (without Br‐coordination) in Cu‐Trz‐Br. As shown in Figure S34, the Br‐coordinated Cu1/Cu2 shows lower energy barriers for initial CO2 adsorption and *COOH formation, compared to that on Cu3. Importantly, Cu1/Cu2 demonstrates the energy barrier of –0.19 eV for *CO formation, much lower than that of 0.97 eV on Cu3. It is believed that the introduction of Br‐coordination to Cu–N4 sites significantly boosts the generation of key *CO intermediate for further C‐C coupling process.

The Gibbs free energies were compared to investigate potential C2+ pathways toward electrocatalytic CO2RR on Cu‐Trz‐Br (Cu1/Cu2) and CuPc. As shown in Figure 6e, the Gibbs free energies change (ΔG) values for initial CO2 adsorption on Cu‐Trz‐Br and CuPc are –1.33 and –0.77 eV, respectively, confirming higher CO2 adsorption capability of Cu‐Trz‐Br [26]. Notably, the hydrogenation of *CO2 on Cu‐Trz‐Br demonstrates a spontaneous trend toward *COOH generation with energy barrier of –0.19 eV, while the formation of *COOH intermediate (ΔG = 0.91 eV) serves as rate‐determining step on CuPc [69]. These results indicate that *CO2 on Cu‐Trz‐Br surface is more energetically activated. The *CO–*CHO coupling has been selected to study C–C dimerization process based on in situ ATR‐FTIR results [70]. Note that the following reduction to *COCHOH on Cu‐Trz‐Br exhibits continuous downhill trend, supporting the efficient generation of C2+ products. Specifically, the hydrogenation of *CO to *CHO on Cu‐Trz‐Br is energetically favored with energy barrier of –0.68 eV, much lower than the 0.67 eV on CuPc. Furthermore, the main competitive reaction of HER trend was also investigated. As shown in Figure 6f, Cu‐Trz‐Br displays higher hydrogen adsorption free energy of 1.36 eV than that of 0.76 eV on CuPc, consistent with the effective suppression of HER process on Cu‐Trz‐Br (Figures 4b and S15) [71, 72].

3. Conclusion

In summary, the rational design of Cu coordination has shown great potential in boosting CO2 electroreduction toward C2+ products. High‐purity Cu‐Trz‐Br nanosheets have been successfully synthesized through one‐pot hydrothermal method, and the crystallographic structure was determined by 3D ED and Rietveld refinement against high‐resolution PXRD data, featuring a unique mixed coordination geometry of Cu–N4Br2 and Cu–N4 sites. The Cu‐Trz‐Br demonstrates excellent FEC2H4 of 56.0% and FEC2+ of 79.4%, much higher than that on Cu‐Trz or CuPc with only Cu–Nx sites. Importantly, Cu‐Trz‐Br also delivers outstanding C2+ production performance under industrial‐level current density. In situ characterizations suggest that modulating the coordination configuration of Cu–N4 sites in Cu‐Trz‐Br greatly promotes the formation of *CO species during CO2RR. DFT calculations further confirm the energetically favored CO2 adsorption/activation and *CO formation on Cu–N4Br2 sites in Cu‐Trz‐Br. It is believed that Cu–N4Br2 dimers possess considerable *CO‐generating capacity and synergistically facilitate C–C coupling toward C2+ products. This work highlights the significance of atomic coordination engineering of catalysts in boosting the electrochemical multiple‐electron transfer reactions.

Author Contributions

Juan Wang: investigation, methodology, data curation, validation, writing – original draft, visualization. Nana Yan: investigation, validation, visualization, data curation. Lutong Shan: investigation, validation, data curation, visualization. Jia Lyu: investigation, data curation, validation, visualization. Qingbo Wa: investigation, data curation. Liang Guo: investigation, data curation. Fengkun Hao: investigation, data curation. Fu Liu: investigation, data curation. Mingzheng Shao: investigation, data curation. Yunhao Wang: investigation, data curation. Guozhi Wang: investigation, data curation. Xiang Meng: investigation, data curation. Chaohui Wang: investigation, data curation. Chenliang Ye: investigation, validation. Yanwei Lum: investigation, validation. Shibo Xi: data curation, investigation, validation. Daliang Zhang: investigation, validation, data curation. Peng Guo: investigation, writing – review and editing, validation, resources, supervision. Zhanxi Fan: conceptualization, investigation, funding acquisition, supervision, resources, project administration, visualization, writing – review and editing.

Conflicts of Interest

The authors declare no conflicts of interest.

Supporting information

CCDC 2325032 for Cu‐Trz‐Br contains the supplementary crystallographic data for this paper. The data can be obtained free of charge via www.ccdc.cam.ac.uk/data_request/cif, or by emailing data_request@ccdc.cam.ac.uk, or by contacting The Cambridge Crystallographic Data Centre, 12 Union Road, Cambridge CB2 1EZ, UK; fax: +44 1223 336033.

Supporting file 1: anie73130‐sup‐0001‐SuppMat.docx.

ANIE-65-e2590405-s001.docx (8.9MB, docx)

Supporting file 1: anie73130‐sup‐0002‐Data.zip.

ANIE-65-e2590405-s002.zip (3.7KB, zip)

Acknowledgments

Z. Fan acknowledges the grant from the National Natural Science Foundation of China (Project No. 22175148), grant from Research Grants Council of Hong Kong (Project No. 21309322), grant from Shenzhen Science and Technology Program (Project No. JCYJ20250604184510013), ITC via Hong Kong Branch of National Precious Metals Material Engineering Research Center, and grants from City University of Hong Kong (Project Nos. 9610480, 9610663, 7020103, 7006007, and 9680301). Y. Lum acknowledges funding from the research project “Development of advanced catalysts for electrochemical carbon abatement, Project Code: 370184872,” a part of the CREATE Thematic Programme in Decarbonisation and supported by the National Research Foundation, Prime Minister's Office, Singapore, under its Campus for Research Excellence and Technological Enterprise (CREATE) programme.

Contributor Information

Peng Guo, Email: pguo@dicp.ac.cn.

Zhanxi Fan, Email: zhanxi.fan@cityu.edu.hk.

Data Availability Statement

The data that support the findings of this study are available from the corresponding author upon reasonable request.

References

  • 1. Yang Y., Louisia S., Yu S., et al., “Operando Studies Reveal Active Cu Nanograins for CO2 Electroreduction,” Nature 614 (2023): 262–269, 10.1038/s41586-022-05540-0. [DOI] [PubMed] [Google Scholar]
  • 2. Cai Y., Yang R., Fu J., et al., “Self‐Pressurizing Nanoscale Capsule Catalysts for CO2 Electroreduction to Acetate or Propanol,” Nature Synthesis 3 (2024): 891–902, 10.1038/s44160-024-00552-2. [DOI] [Google Scholar]
  • 3. Zhang Y., Chen F., Yang X., et al., “Electronic Metal‐Support Interaction Modulates Cu Electronic Structures for CO2 Electroreduction to Desired Products,” Nature Communications 16 (2025): 1956, 10.1038/s41467-025-57307-6. [DOI] [PMC free article] [PubMed] [Google Scholar]
  • 4. Zhou J., Wang T., Chen L., et al., “Boosting the Reaction Kinetics in Aprotic Lithium‐Carbon Dioxide Batteries With Unconventional Phase Metal Nanomaterials,” PNAS 119 (2022): e2204666119. [DOI] [PMC free article] [PubMed] [Google Scholar]
  • 5. Liu F. and Fan Z., “Defect Engineering of Two‐Dimensional Materials for Advanced Energy Conversion and Storage,” Chemical Society Review 52 (2023): 1723–1772, 10.1039/D2CS00931E. [DOI] [PubMed] [Google Scholar]
  • 6. Wang J., Tan H., Xu H., et al., “Electronic Structure Modulation of Unconventional Phase Metal Nanomaterials for Highly Selective Carbon Dioxide Electroreduction,” ACS Materials Letters 5 (2023): 3212–3221, 10.1021/acsmaterialslett.3c01156. [DOI] [Google Scholar]
  • 7. Wang J., Yu J., Sun M., et al., “Surface Molecular Functionalization of Unusual Phase Metal Nanomaterials for Highly Efficient Electrochemical Carbon Dioxide Reduction Under Industry‐Relevant Current Density,” Small 18 (2022): 2106766. [DOI] [PubMed] [Google Scholar]
  • 8. Yu J., Wang J., Ma Y., et al., “Recent Progresses in Electrochemical Carbon Dioxide Reduction on Copper‐Based Catalysts toward Multicarbon Products,” Advanced Functional Materials 31 (2021): 2102151, 10.1002/adfm.202102151. [DOI] [Google Scholar]
  • 9. Ma Y., Wang J., Yu J., et al., “Surface Modification of Metal Materials For High‐Performance Electrocatalytic Carbon Dioxide Reduction,” Matter 4 (2021): 888–926. [Google Scholar]
  • 10. Zeng M., Fang W., Cen Y., Zhang X., Hu Y., and Xia B. Y., “Reaction Environment Regulation for Electrocatalytic CO2 Reduction in Acids,” Angewandte Chemie International Edition 63 (2024): e202404574, 10.1002/anie.202404574. [DOI] [PubMed] [Google Scholar]
  • 11. Xia C., Wang X., He C., et al., “Highly Selective Electrocatalytic CO2 Conversion to Tailored Products Through Precise Regulation of Hydrogenation and C–C Coupling,” Journal of the American Chemical Society 146 (2024): 20530–20538, 10.1021/jacs.4c07502. [DOI] [PubMed] [Google Scholar]
  • 12. Chen R., Wu Q., Zhu J., et al., “Hydrophobic Ionic Liquid Engineering for Reversing CO Intermediate Configuration Toward Ampere‐Level CO2 Electroreduction to C2+ Products,” Journal of the American Chemical Society 147 (2025): 7921–7931, 10.1021/jacs.4c18508. [DOI] [PubMed] [Google Scholar]
  • 13. Saha P., Amanullah S., and Dey A., “Selectivity in Electrochemical CO2 Reduction,” Accounts of Chemical Research 55 (2022): 134–144, 10.1021/acs.accounts.1c00678. [DOI] [PubMed] [Google Scholar]
  • 14. Wang J., Liu J., Song Y., et al., “Simultaneous Defect and Size Control of Metal–Organic Framework Nanostructures for Highly Efficient Carbon Dioxide Electroreduction to Multicarbon Products,” ACS Materials Letters 5 (2023): 2121–2130, 10.1021/acsmaterialslett.3c00567. [DOI] [Google Scholar]
  • 15. Zhu Y., Cui X., Liu H., et al., “Tandem Catalysis in Electrochemical CO2 Reduction Reaction,” Nano Research 14 (2021): 4471–4486, 10.1007/s12274-021-3448-2. [DOI] [Google Scholar]
  • 16. Birdja Y. Y., Pérez‐Gallent E., Figueiredo M. C., Göttle A. J., Calle‐Vallejo F., and Koper M. T. M., “Advances and Challenges in Understanding the Electrocatalytic Conversion of Carbon Dioxide to Fuels,” Nature Energy 4 (2019): 732–745, 10.1038/s41560-019-0450-y. [DOI] [Google Scholar]
  • 17. Zheng Y., Vasileff A., Zhou X., Jiao Y., Jaroniec M., and Qiao S. Z., “Understanding the Roadmap for Electrochemical Reduction of CO2 to Multi‐Carbon Oxygenates and Hydrocarbons on Copper‐Based Catalysts,” Journal of the American Chemical Society 141 (2019): 7646–7659, 10.1021/jacs.9b02124. [DOI] [PubMed] [Google Scholar]
  • 18. Cao Y., Chen Z., Li P., et al., “Surface Hydroxide Promotes CO2 Electrolysis to Ethylene in Acidic Conditions,” Nature Communications 14 (2023): 2387, 10.1038/s41467-023-37898-8. [DOI] [PMC free article] [PubMed] [Google Scholar]
  • 19. Xie X., Zhang X., Xie M., et al., “Au‐Activated N Motifs in Non‐coherent Cupric Porphyrin Metal Organic Frameworks for Promoting and Stabilizing Ethylene Production,” Nature Communications 13 (2022): 63, 10.1038/s41467-021-27768-6. [DOI] [PMC free article] [PubMed] [Google Scholar]
  • 20. He Q., Li H., Hu Z., Lei L., Wang D., and Li T. T., “Highly Selective CO2 Electroreduction to C2H4 Using a Dual‐Sites Cu(II) Porphyrin Framework Coupled with Cu2O Nanoparticles via a Synergetic‐Tandem Strategy,” Angewandte Chemie International Edition 63 (2024): e202407090, 10.1002/anie.202407090. [DOI] [PubMed] [Google Scholar]
  • 21. Chen X., Jia S., Zhai J., et al., “Multivalent Cu Sites Synergistically Adjust Carbonaceous Intermediates Adsorption for Electrocatalytic Ethanol Production,” Nature Communications 15 (2024): 7691, 10.1038/s41467-024-51928-z. [DOI] [PMC free article] [PubMed] [Google Scholar]
  • 22. Han C., Yang T., Fang Y., et al., “Steering the Product Selectivity of CO2 Electroreduction by Single Atom Switching in Isostructural Copper Nanocluster Catalysts,” Angewandte Chemie International Edition 64 (2025): e202503417. [DOI] [PubMed] [Google Scholar]
  • 23. Lian Z., Dattila F., and López N., “Stability and Lifetime of Diffusion‐Trapped Oxygen in Oxide‐Derived Copper CO2 Reduction Electrocatalysts,” Nature Catalysis 7 (2024): 401–411, 10.1038/s41929-024-01132-5. [DOI] [Google Scholar]
  • 24. O'Brien C. P., Miao R. K., Shayesteh Zeraati A., Lee G., Sargent E. H., and Sinton D., “CO2 Electrolyzers,” Chemical Reviews 124 (2024): 3648–3693, 10.1021/acs.chemrev.3c00206. [DOI] [PubMed] [Google Scholar]
  • 25. Pimlott D. J. D., Kim Y., and Berlinguette C. P., “Reactive Carbon Capture Enables CO2 Electrolysis With Liquid Feedstocks,” Accounts of Chemical Research 57 (2024): 1007–1018, 10.1021/acs.accounts.3c00571. [DOI] [PubMed] [Google Scholar]
  • 26. Tan Z., Zhang J., Yang Y., et al., “Polymeric Ionic Liquid Promotes Acidic Electrocatalytic CO2 Conversion to Multicarbon Products with Ampere Level Current on Cu,” Nature Communications 16 (2025): 1843, 10.1038/s41467-025-57095-z. [DOI] [PMC free article] [PubMed] [Google Scholar]
  • 27. Franco F., Rettenmaier C., Jeon H. S., and Cuenya B. R., “Transition Metal‐Based Catalysts for the Electrochemical CO2 Reduction: From Atoms and Molecules to Nanostructured Materials,” Chemical Society Reviews 49 (2020): 6884–6946, 10.1039/D0CS00835D. [DOI] [PubMed] [Google Scholar]
  • 28. Zhang R.‐Z., Wu B.‐Y., Li Q., Lu L.‐L., Shi W., and Cheng P., “Design Strategies and Mechanism Studies of CO2 Electroreduction Catalysts Based on Coordination Chemistry,” Coordination Chemistry Reviews 422 (2020): 213436, 10.1016/j.ccr.2020.213436. [DOI] [Google Scholar]
  • 29. Huang J.‐M., Zhang X.‐D., Huang J.‐Y., Zheng D.‐S., Xu M., and Gu Z.‐Y., “MOF‐Based Materials for Electrochemical Reduction of Carbon Dioxide,” Coordination Chemistry Reviews 494 (2023): 215333, 10.1016/j.ccr.2023.215333. [DOI] [Google Scholar]
  • 30. Wang C., Lv Z., Yang W., Feng X., and Wang B., “A Rational Design of Functional Porous Frameworks for Electrocatalytic CO2 Reduction Reaction,” Chemical Society Reviews 52 (2023): 1382–1427, 10.1039/D2CS00843B. [DOI] [PubMed] [Google Scholar]
  • 31. Mamaghani A. H., Liu J., Zhang Z., et al., “Promises of MOF‐Based and MOF‐Derived Materials for Electrocatalytic CO2 Reduction,” Advanced Energy Materials 14 (2024): 2402278, 10.1002/aenm.202402278. [DOI] [Google Scholar]
  • 32. Peng Y., Sanati S., Morsali A., and Garcia H., “Metal–Organic Frameworks as Electrocatalysts,” Angewandte Chemie International Edition 62 (2023): e202214707, 10.1002/anie.202214707. [DOI] [PubMed] [Google Scholar]
  • 33. Yang F., Zhu D., Xia C., Shahid Z., Chen S., and Xia B. Y., “Copper‐Organic Frameworks for Electrocatalytic Carbon Dioxide Reduction,” Coordination Chemistry Reviews 517 (2024): 216021, 10.1016/j.ccr.2024.216021. [DOI] [Google Scholar]
  • 34. Yang D., Ni B., and Wang X., “Heterogeneous Catalysts with Well‐Defined Active Metal Sites Toward CO2 Electrocatalytic Reduction,” Advanced Energy Materials 10 (2020): 2001142, 10.1002/aenm.202001142. [DOI] [Google Scholar]
  • 35. Song D., Lian Y., Wang M., et al., “Electrochemical CO2 Reduction Catalyzed by Organic/Inorganic Hybrids,” eScience 3 (2023): 100097, 10.1016/j.esci.2023.100097. [DOI] [Google Scholar]
  • 36. Shah S. S. A., Najam T., Wen M., Zang S.‐Q., Waseem A., and Jiang H.‐L., “Metal–Organic Framework‐Based Electrocatalysts for CO2 Reduction,” Small Structures 3 (2021): 2100090, 10.1002/sstr.202100090. [DOI] [Google Scholar]
  • 37. Weng Z., Jiang J., Wu Y., et al., “Electrochemical CO2 Reduction to Hydrocarbons on a Heterogeneous Molecular Cu Catalyst in Aqueous Solution,” Journal of the American Chemical Society 138 (2016): 8076–8079, 10.1021/jacs.6b04746. [DOI] [PubMed] [Google Scholar]
  • 38. Wang J., Wa Q., Diao Q., et al., “Atomic Design of Copper Active Sites in Pristine Metal–Organic Coordination Compounds for Electrocatalytic Carbon Dioxide Reduction,” Small Methods 8 (2024): 2400432. [DOI] [PMC free article] [PubMed] [Google Scholar]
  • 39. Wang Y. R., Ding H. M., Ma X. Y., et al., “Imparting CO2 Electroreduction Auxiliary for Integrated Morphology Tuning and Performance Boosting in a Porphyrin‐Based Covalent Organic Framework,” Angewandte Chemie International Edition 61 (2022): e202114648, 10.1002/anie.202114648. [DOI] [PubMed] [Google Scholar]
  • 40. Wang Y. R., Liu M., Gao G. K., et al., “Implanting Numerous Hydrogen‐Bonding Networks in a Cu‐Porphyrin‐Based Nanosheet to Boost CH4 Selectivity in Neutral‐Media CO2 Electroreduction,” Angewandte Chemie International Edition 60 (2021): 21952–21958, 10.1002/anie.202108388. [DOI] [PubMed] [Google Scholar]
  • 41. Wang J., Sun M., Xu H., et al., “Coordination Environment Engineering of Metal Centers in Coordination Polymers for Selective Carbon Dioxide Electroreduction toward Multicarbon Products,” ACS Nano 18 (2024): 7192–7203, 10.1021/acsnano.3c12389. [DOI] [PubMed] [Google Scholar]
  • 42. Zhuo L. L., Chen P., Zheng K., et al., “Flexible Cuprous Triazolate Frameworks as Highly Stable and Efficient Electrocatalysts for CO2 Reduction with Tunable C2H4/CH4 Selectivity,” Angewandte Chemie International Edition 61 (2022): e202204967, 10.1002/anie.202204967. [DOI] [PubMed] [Google Scholar]
  • 43. Zhu H. L., Huang J. R., Liao P. Q., and Chen X. M., “Rational Design of Metal–Organic Frameworks for Electroreduction of CO2 to Hydrocarbons and Carbon Oxygenates,” ACS Central Science 8 (2022): 1506–1517, 10.1021/acscentsci.2c01083. [DOI] [PMC free article] [PubMed] [Google Scholar]
  • 44. Chen Q., Zhou G., and Huang Z., “Single‐Crystal Structural Analysis of 2D Metal–Organic Frameworks and Covalent Organic Frameworks by Three‐Dimensional Electron Diffraction,” Accounts of Chemical Research 57 (2024): 2522–2531, 10.1021/acs.accounts.4c00335. [DOI] [PMC free article] [PubMed] [Google Scholar]
  • 45. Ge M., Wang Y., Carraro F., et al., “High‐Throughput Electron Diffraction Reveals a Hidden Novel Metal–Organic Framework for Electrocatalysis,” Angewandte Chemie International Edition 60 (2021): 11391–11397, 10.1002/anie.202016882. [DOI] [PMC free article] [PubMed] [Google Scholar]
  • 46. Huang Z., Grape E. S., Li J., Inge A. K., and Zou X., “3D electron Diffraction as an Important Technique for Structure Elucidation of Metal‐Organic Frameworks and Covalent Organic Frameworks,” Coordination Chemistry Reviews 427 (2021): 213583, 10.1016/j.ccr.2020.213583. [DOI] [Google Scholar]
  • 47. Jin F. Z., Lin E., Wang T. H., et al., “Rationally Fabricating 3D Porphyrinic Covalent Organic Frameworks With scu Topology as Highly Efficient Photocatalysts,” Chemistry 8 (2022): 3064–3080, 10.1016/j.chempr.2022.07.016. [DOI] [Google Scholar]
  • 48. Yang Y., Lin E., Wang S., Wang T., Wang Z., and Zhang Z., “Single‐Crystal One‐Dimensional Porous Ladder Covalent Polymers,” Journal of the American Chemical Society 146 (2024): 782–790, 10.1021/jacs.3c10812. [DOI] [PubMed] [Google Scholar]
  • 49. Wang J., Ma C., Liu J., et al., “Pure Silica With Ordered Silanols for Propylene/Propane Adsorptive Separation Unraveled by Three‐Dimensional Electron Diffraction,” Journal of the American Chemical Society 145 (2023): 6853–6860, 10.1021/jacs.2c13847. [DOI] [PubMed] [Google Scholar]
  • 50. Nie C., Yan N., Liao C., et al., “Unraveling a Stable 16‐Ring Aluminophosphate DNL‐11 Through Three‐Dimensional Electron Diffraction for Atmospheric Water Harvesting,” Journal of the American Chemical Society 146 (2024): 10257–10262, 10.1021/jacs.4c01393. [DOI] [PubMed] [Google Scholar]
  • 51. Zhang D., Oleynikov P., Hovmöller S., and Zou X., “Collecting 3D Electron Diffraction Data by the Rotation Method,” Zeitschrift Fur Kristallograhie 225 (2010): 94–102, 10.1524/zkri.2010.1202. [DOI] [Google Scholar]
  • 52. Kolb U., Krysiak Y., and Plana‐Ruiz S., “Automated Electron Diffraction Tomography – Development and Applications,” Acta Crystallographica B 75 (2019): 463–474. [DOI] [PMC free article] [PubMed] [Google Scholar]
  • 53. Yang T., Willhammar T., Xu H., Zou X., and Huang Z., “Single‐Crystal Structure Determination of Nanosized Metal–Organic Frameworks by Three‐Dimensional Electron Diffraction,” Nature Protocols 17 (2022): 2389–2413, 10.1038/s41596-022-00720-8. [DOI] [PubMed] [Google Scholar]
  • 54. Ling Y., Sun T., Guo L., et al., “Atomic‐level Structural Responsiveness to Environmental Conditions from 3D Electron Diffraction,” Nature Communications 13 (2022): 6625, 10.1038/s41467-022-34237-1. [DOI] [PMC free article] [PubMed] [Google Scholar]
  • 55. Kabsch W., “XDS,” Acta Crystallographica D 66 (2010): 125–132. [DOI] [PMC free article] [PubMed] [Google Scholar]
  • 56. Sheldrick G. M., “A Short History of SHELX,” Acta Crystallographica A 64 (2008): 112–122, 10.1107/S0108767307043930. [DOI] [PubMed] [Google Scholar]
  • 57. Yang K., Sun Y., Chen S., et al., “Less‐Coordinated Atomic Copper‐Dimer Boosted Carbon–Carbon Coupling during Electrochemical CO2 Reduction,” Small 19 (2023): 2301536, 10.1002/smll.202301536. [DOI] [PubMed] [Google Scholar]
  • 58. Zheng M., Wang P., Zhi X., et al., “Electrocatalytic CO2‐to‐C2+ With Ampere‐Level Current on Heteroatom‐Engineered Copper via Tuning *CO Intermediate Coverage,” Journal of the American Chemical Society 144 (2022): 14936–14944, 10.1021/jacs.2c06820. [DOI] [PubMed] [Google Scholar]
  • 59. Wang P., Yang H., Tang C., et al., “Boosting Electrocatalytic CO2–to–Ethanol Production via Asymmetric C–C Coupling,” Nature Communications 13 (2022): 3754, 10.1038/s41467-022-31427-9. [DOI] [PMC free article] [PubMed] [Google Scholar]
  • 60. Liang Y., Zhao J., Yang Y., et al., “Stabilizing Copper Sites in Coordination Polymers Toward Efficient Electrochemical C‐C Coupling,” Nature Communications 14 (2023): 474, 10.1038/s41467-023-35993-4. [DOI] [PMC free article] [PubMed] [Google Scholar]
  • 61. Zhang L., Li X. X., Lang Z. L., et al., “Enhanced Cuprophilic Interactions in Crystalline Catalysts Facilitate the Highly Selective Electroreduction of CO2 to CH4 ,” Journal of the American Chemical Society 143 (2021): 3808–3816, 10.1021/jacs.0c11450. [DOI] [PubMed] [Google Scholar]
  • 62. Zhang W., Huang C., Xiao Q., et al., “Atypical Oxygen‐Bearing Copper Boosts Ethylene Selectivity Toward Electrocatalytic CO2 Reduction,” Journal of the American Chemical Society 142 (2020): 11417–11427, 10.1021/jacs.0c01562. [DOI] [PubMed] [Google Scholar]
  • 63. Bodappa N., Su M., Zhao Y., et al., “Early Stages of Electrochemical Oxidation of Cu(111) and Polycrystalline Cu Surfaces Revealed by In Situ Raman Spectroscopy,” Journal of the American Chemical Society 141 (2019): 12192–12196, 10.1021/jacs.9b04638. [DOI] [PubMed] [Google Scholar]
  • 64. Arán‐Ais R. M., Scholten F., Kunze S., Rizo R., and Cuenya B. R., “The Role of In Situ Generated Morphological Motifs and Cu(i) Species in C2+ Product Selectivity During CO2 Pulsed Electroreduction,” Nature Energy 5 (2020): 317–325, 10.1038/s41560-020-0594-9. [DOI] [Google Scholar]
  • 65. Wang X., Klingan K., Klingenhof M., et al., “Morphology and Mechanism of Highly Selective Cu(II) Oxide Nanosheet Catalysts for Carbon Dioxide Electroreduction,” Nature Communications 12 (2021): 794, 10.1038/s41467-021-20961-7. [DOI] [PMC free article] [PubMed] [Google Scholar]
  • 66. Ma Y., Sun M., Xu H., et al., “Site‐Selective Growth of fcc‐2H‐fcc Copper on Unconventional Phase Metal Nanomaterials for Highly Efficient Tandem CO2 Electroreduction,” Advanced Materials 36 (2024): 2402979, 10.1002/adma.202402979. [DOI] [PubMed] [Google Scholar]
  • 67. Wang C. L., Lv Z. H., Feng X., Yang W. X., and Wang B., “Adjacent Metal Atomic Pairs Within Atomically Dispersed Catalysts for Reaching a Synergistic Electrocatalytic CO2 Reduction: A Review,” Advanced Energy Materials 14 (2024): 2400160, 10.1002/aenm.202400160. [DOI] [Google Scholar]
  • 68. Chen S., Zheng X., Zhu P., et al., “Copper Atom Pairs Stabilize *OCCO Dipole toward Highly Selective CO2 Electroreduction to C2H4 ,” Angewandte Chemie International Edition 63 (2024): e202411591, 10.1002/anie.202411591. [DOI] [PubMed] [Google Scholar]
  • 69. Wang Y., Wang J., Cai R., et al., “Enhanced Local CO Coverage on Cu Quantum Dots for Boosting Electrocatalytic CO2 Reduction to Ethylene,” Advanced Functional Materials 34 (2024): 2417764. [Google Scholar]
  • 70. Qiu X. F., Zhu H. L., Huang J. R., Liao P. Q., and Chen X. M., “Highly Selective CO2 Electroreduction to C2H4 Using a Metal–Organic Framework with Dual Active Sites,” Journal of the American Chemical Society 143 (2021): 7242–7246, 10.1021/jacs.1c01466. [DOI] [PubMed] [Google Scholar]
  • 71. Abghoui Y. and Skúlason E., “Hydrogen Evolution Reaction Catalyzed by Transition‐Metal Nitrides,” Journal of Physical Chemistry C 121 (2017): 24036–24045, 10.1021/acs.jpcc.7b06811. [DOI] [Google Scholar]
  • 72. Zhou Y., Zhang J., Song E., et al., “Enhanced Performance of In‐Plane Transition Metal Dichalcogenides Monolayers by Configuring Local Atomic Structures,” Nature Communications 11 (2020): 2253, 10.1038/s41467-020-16111-0. [DOI] [PMC free article] [PubMed] [Google Scholar]

Associated Data

This section collects any data citations, data availability statements, or supplementary materials included in this article.

Supplementary Materials

CCDC 2325032 for Cu‐Trz‐Br contains the supplementary crystallographic data for this paper. The data can be obtained free of charge via www.ccdc.cam.ac.uk/data_request/cif, or by emailing data_request@ccdc.cam.ac.uk, or by contacting The Cambridge Crystallographic Data Centre, 12 Union Road, Cambridge CB2 1EZ, UK; fax: +44 1223 336033.

Supporting file 1: anie73130‐sup‐0001‐SuppMat.docx.

ANIE-65-e2590405-s001.docx (8.9MB, docx)

Supporting file 1: anie73130‐sup‐0002‐Data.zip.

ANIE-65-e2590405-s002.zip (3.7KB, zip)

Data Availability Statement

The data that support the findings of this study are available from the corresponding author upon reasonable request.

Articles from Angewandte Chemie (International Ed. in English) are provided here courtesy of Wiley

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