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BiVO4 as a precatalyst for CO2 electroreduction to formate at large current density
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Longsheng Zhan1, Yuchao Wang1, Mengjie Liu1, Xin Zhao, Danni Deng, Xinran Zheng, Jiabi Jiang, Xiang Xiong, Yongpeng Lei*
Chinese Chemical Letters | 2025, 36(3) : 109695
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Chinese Chemical Letters | 2025, 36(3): 109695
• Communication •
BiVO4 as a precatalyst for CO2 electroreduction to formate at large current density
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Longsheng Zhan1, Yuchao Wang1, Mengjie Liu1, Xin Zhao, Danni Deng, Xinran Zheng, Jiabi Jiang, Xiang Xiong, Yongpeng Lei*
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  • State Key Laboratory of Powder Metallurgy, Central South University, Changsha 410083, China
Published: 2025-03-15 doi: 10.1016/j.cclet.2024.109695
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The large current density of electrochemical CO2 reduction towards industrial application is challenging. Herein, without strong acid and reductant, the synthesized BiVO4 with abundant oxygen vacancies (Ovs) exhibited a high formate Faradaic efficiency (FE) of 97.45% (-0.9 V) and a large partial current density of -45.82 mA/cm2 (-1.2 V). The good performance benefits from the reconstruction of BiVO4 to generate active metal Bi sites, which results in the electron redistribution to boost the OCHO* formation. In flow cells, near industrial current density of 183.94 mA/cm2 was achieved, with the FE of formate above 95% from 20 mA/cm2 to 180 mA/cm2. Our work provides a facily synthesized BiVO4 precatalyst for CO2 electroreduction.

CO2 electroreduction  /  Bismuth vanadate  /  Formate  /  Oxygen vacancies  /  Large current density
Longsheng Zhan, Yuchao Wang, Mengjie Liu, Xin Zhao, Danni Deng, Xinran Zheng, Jiabi Jiang, Xiang Xiong, Yongpeng Lei. BiVO4 as a precatalyst for CO2 electroreduction to formate at large current density[J]. Chinese Chemical Letters, 2025 , 36 (3) : 109695 - . DOI: 10.1016/j.cclet.2024.109695
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As one of the most attractive approaches to achieve carbon peaking and carbon neutralization, electrochemical CO2 reduction reaction (CO2RR) receives widespread attention [1-4]. Generally, products of CO2RR can be divided into C1 (CO, HCOO−, etc.) [5-7] and C2+ (C2H4, C2H5OH, etc.) [8-11]. Technical and economic analysis indicates that formic acid/formate are the most valuable product, which are important industrial raw materials and fuels for fuel cells [12-14]. Compared with other metallic materials, such as Pd, In, and Sn, bismuth (Bi)-based materials are potential candidates due to the effective inhibition of competitive hydrogen evolution reaction during CO2RR [15].
Recently, some modulation strategies have been applied to improve the performance of CO2RR [16,17], such as the two-dimensional transformation [18], interface construction [19], defect engineering [20,21], and element doping [22]. For instance, catalyst reconstruction could effectively modulate the local electronic structure of active sites, which was beneficial for the adsorption and conversion of CO2 molecules [23]. However, the reconstruction process of BiVO4 with oxygen vacancies (Ovs) was rarely noted in electrocatalytic CO2 reduction.
Herein, BiVO4 was synthesized by a relatively simple process (no strong acids and strong reductant) (Table S1 in Supporting information). As a precatalyst, the optimized sample (BV-2) reconstructed into active metal Bi during the reaction process, which presented the maximum formate selectivity of 97.45% at −0.9 V and a large partial current density of −45.82 mA/cm2 at −1.2 V. In two-electrode flow cells, the formate selectivity maintained ~95% from 20 mA/cm2 to 180 mA/cm2, and the maximum partial current density could reach 175.23 mA/cm2 at 2.8 V.
As shown in Fig. 1a, a series of BiVO4 (BV) were synthesized by a hydrothermal strategy. The difference among them is the amount of sodium dodecyl sulfonate (SDS) during prepared process. BV-0, BV-1, BV-2 and BV-3 were constructed via adding 0, 0.1, 0.2 and 0.3 g SDS, respectively. It is clear that there was no significant difference in the color of the series of samples as shown in Fig. S1. The X-ray diffraction (XRD) patterns in Fig. 1b showed that the phase of BiVO4 was multiple crystal structures. BV-0, BV-1 and BV-2 were consistent with monoclinic BiVO4 (m-BiVO4, PDF#14–0688) and tetragonal BiVO4 (t-BiVO4, PDF#14–0133). When adding 0.3 g SDS, additional crystal phase ascribed to tetragonal structure (PDF#49–0198) in XRD of BV-3. The highest diffraction peak at 24.4° in XRD of BV-2 was corresponding to the BiVO4 (200) tetragonal structure (PDF#14–0133). However, the highest diffraction peak at 28.9° of other samples was BiVO4 (121), which was consistent with monoclinic structure (PDF#14–0688).
Fourier transform infrared (FT-IR) spectra (Fig. S2 in Supporting information) were aimed to explore the functional groups in BiVO4. The strong peak of 749 cm−1 was assigned to the asymmetric stretching of VO43−, revealing successful synthesis of BiVO4 [24]. Raman spectra (Fig. 1c) were investigated to verify the structure of BiVO4 [25]. The bands at 211, 326, 368 and 827 cm−1 were assigned to the vibrations of monoclinic BiVO4 [26]. The additional shoulder band at 853 cm−1 was ascribed to the symmetric stretching mode of V-O band for tetragonal BiVO4 [27]. It meant that the prepared samples were the mixed crystalline structure of BiVO4, which was in compliance with XRD results. The band at 246 cm−1 of BV-2 was attributed to Ovs. We suppose that adding SDS could introduce Ovs in BiVO4 [28].
To investigate the chemical valence states and compositions of BV species, the X-ray photoelectron spectroscopy (XPS) measurement was employed. The survey spectra were shown in Fig. S3 (Supporting information), indicating co-existences of Bi, V and O elements. As shown in Bi 4f XPS spectra (Fig. 2a), for BV-0, two peaks at 164.2 and 158.9 eV were corresponded to Bi 4f5/2 and Bi 4f7/2, respectively, implying the valence of Bi was +3. Compared with BV-0, characteristic peaks of BV-2 showed a slight shift to low binding energy. Moreover, two characteristic peaks of BV-2 in V 2p spectra also showed a slight shift (~0.1 eV) to low binding energy (Fig. S4 in Supporting information). As shown in Fig. 2b, the high-resolution O 1s XPS spectra were deconvoluted into three peaks with the lattice oxygen, surface hydroxyls and adsorbed oxygen, corresponding to the binding energies of 533, 530.9 and 529.4 eV, respectively. The surface hydroxyls (OH) were related to the dissociative adsorption of water with Ovs. BV-2 displayed more OH, indicating more Ovs, which were calculated based on the area of peaks (Table S2 in Supporting information) [29]. The slight shift of Bi 4f and V 2p XPS spectra, was possibly due to the different chemical environment caused by Ovs.
In order to further confirm the existence of Ovs, electron paramagnetic resonance (EPR) was employed (Fig. 2c). Paramagnetic signal at g = 2.004 was characteristics of Ovs. Compared to BV-0, the peak intensity of BV-2 was enhanced, which might improve the mobility of electrons. The crystal structure was disclosed by high-resolution transmission electron microscope (HRTEM). In Fig. S5 (Supporting information), BV-2 revealed lattices fringes with interatomic distance of 0.269 nm for the (112) plane of t-BiVO4 and 0.308 nm for the (121) plane of m-BiVO4. The interface (labeled by pink line) between t-BiVO4 and m-BiVO4 was observed. Meanwhile, BV-0 exhibited the (121) plane of m-BiVO4 with lattices fringes of 0.308 nm (Fig. S6 in Supporting information). No planes of t-BiVO4 were found. The energy dispersive spectra (EDS) elemental mapping images of BV-2 and BV-0 were presented in Fig. 2d and Fig. S7 (Supporting information). The results revealed the uniform distribution of Bi, V and O elements.
To evaluate the CO2RR performance of electrocatalysts, H-type cells were applied with 0.5 mol/L KHCO3 as electrolyte [30]. All the potential was referred to the reversible hydrogen electrode (RHE). The commercial Bi powder (C-Bi) with the size of 200 mesh was selected for comparison. Firstly, we tested the linear sweep voltammetry (LSV) curves at different saturated atmosphere (Ar and CO2). The difference of curves indicated their CO2 conversion capacity (Fig. S8 in Supporting information) [31]. As displayed by LSV curves in CO2-saturated atmosphere in Fig. 3a, the current density of BV-2 sharply increased and markedly reached −49.16 mA/cm2 at −1.2 V, which was larger than that of other samples. To figure out their activity and selectivity towards CO2RR, the constant voltage electrolysis was carried out (Fig. S9 in Supporting information). HCOO− was the main products from CO2RR for BV species (Fig. S10 in Supporting information). In Fig. 3b, the formate Faradaic efficiency (FEHCOO-) of BV-2 was greater than 90% from −0.8 V to −1.2 V, which could arrive 97.45% at −0.9 V. Fig. 3c showed the comparison of FEHCOO- with other samples (BV-0, BV-1, BV-3 and C-Bi), founding that BV-2 displayed the highest FEHCOO- and widest voltage window. Also, BV-2 achieved a maximum JHCOO- of −45.82 mA/cm2@−1.2 V, while the JHCOO- of C-Bi was −13.42 mA/cm2@−1.2 V (Fig. 3d). BV-2 at −1.0 V could reach a stability of 40 h and FEHCOO- of 85.8% (inset of Fig. 3d). Fig. 3e and Table S3 (Supporting information) gave a summary of up-to-date Bi-based catalysts for JHCOO- in H-type cells. BV-2 outperformed most of reported electrocatalysts for CO2RR.
In-situ Raman spectra were further investigated (Figs. 4a and b). As the electrolysis proceeded, Bi-Bi bands were appeared at 63 and 84 cm−1 [32]. It meant that BV-2 acted as a precatalyst. During the electrolysis process, BV-2 underwent surface reconstruction to produce metal Bi, which consisted with the XRD and XPS results of BV-2 after reaction (Figs. S11 and S12 in Supporting information). Then the peak at 1540 cm−1 was stronger with prolonged time, which could be assigned to asymmetric C—O stretching vibration of OCHO* intermediate [33]. The reconstruction process induced a redistribution of charges, promoting the conversion of CO2 molecules. Then we explored the electrochemical active surface areas (ECSA), which was evaluated by the electric double-layer capacitance (Cdl) method (Fig. S13 in Supporting information) [34,35]. As shown in Fig. S14a (Supporting information), BV-2 had the larger Cdl with 1090 µF/cm2 than other samples, corresponding to larger ECSA. Also, Cdl of BV-0 (497 µF/cm2), BV-1 (585 µF/cm2) and BV-3 (652 µF/cm2) were greater than that of C-Bi (304 µF/cm2). In Fig. S14b (Supporting information), the Tafel slope was ~178.1 mV/dec of BV-2, significantly lower than ~201.7 mV/dec for BV-0, indicating faster reaction kinetics [36,37]. The electrochemical impedance spectroscopy (EIS) was conducted. The EIS results and the corresponding equivalent circuit was presented in Fig. 4c. BV-2 demonstrated the smallest charge-transfer resistance than other contrast samples (Table S4 in Supporting information), enabling the largest current density of formate.
Furthermore, the CO2RR performance in flow cells was evaluated [38]. Nickle foam was used as anode and BV-2 supported on gas diffusion layer was used as cathode. When changing the saturated atmosphere from Ar to CO2, the current density in LSV curves was increased, indicating that excellent CO2 activity (Fig. S15 in Supporting information) [39]. The maximum current density arrived 183.94 mA/cm2 at 2.8 V, which was closed to industrial-scale current density [40]. The JHCOO- of BV-2 could reach 175.23 mA/cm2 at 2.8 V as well as the FEHCOO- remain around 95% from 20 mA/cm2 to 180 mA/cm2 (Fig. 4d and Fig. S16 in Supporting information).
In summary, BiVO4 with Ovs was constructed through a relatively simple synthesis approach, which acted as a precatalyst for CO2RR. The BV-2 achieved high FEHCOO-, large JHCOO- of −45.82 mA/cm2 (−1.2 V) in H-type cells and near industrial current density in flow cells.
Declaration of competing interest
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The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper.
Acknowledgments
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This work was financially supported by the Fundamental Research Funds for the Central Universities of Central South University (No. 2022ZZTS0579).
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Year 2025 volume 36 Issue 3
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doi: 10.1016/j.cclet.2024.109695
  • Receive Date：2024-01-21
  • Online Date：2025-11-07
  • Published：2025-03-15
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  • Received：2024-01-21
  • Revised：2024-02-18
  • Accepted：2024-02-26
Affiliations
    State Key Laboratory of Powder Metallurgy, Central South University, Changsha 410083, China
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表12种不同金属材料的力学参数
科
Family		 属数
Number of
genus		 种数
Number of
species		 占总种数比例
Percentage of
total species (%)		 属
Genus		 种数
Number of
species		 占总种数比例
Percentage of total
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鹅膏菌科Amanitaceae 2 11 5.26 鹅膏菌属 Amanita 10 4.78
小菇科 Mycenaceae 2 12 5.74 丝盖伞属 Inocybe 5 2.39
多孔菌科 Polyporaceae 8 14 6.70 蜡蘑属 Laccaria 5 2.39
红菇科 Russulaceae 3 23 11.00 小皮伞属 Marasmius 6 2.87
小菇属 Mycena 11 5.26
光柄菇属 Pluteus 5 2.39
红菇属 Russula 17 8.13
栓菌属 Trametes 5 2.39
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