Abstract It remains a challenge to identify the active sites of bismuth catalysts in the electrochemical CO 2 reduction reaction. Here we show through in situ characterization that the activation of bismuth oxyhalide electrocatalysts to metallic bismuth is guided by the halides. In situ X-ray diffraction results show that bromide promotes the selective exposure of planar bismuth surfaces, whereas chloride and iodide result in more disordered active sites. Furthermore, we find that bromide-activated bismuth catalysts outperform the chloride and iodide counterparts, achieving high current density (&gt;100 mA cm –2 ) and formic acid selectivity (&gt;90%), suggesting that planar bismuth surfaces are more active for the electrochemical CO 2 reduction reaction. In addition, in situ X-ray absorption spectroscopy measurements reveal that the reconstruction proceeds rapidly in chloride-activated bismuth and gradually when bromide is present, facilitating the formation of ordered planar surfaces. These findings show the pivotal role of halogens on selective facet exposure in activated bismuth-based electrocatalysts during the electrochemical CO 2 reduction reaction. 

Halide-guided active site exposure in bismuth electrocatalysts for selective CO2 conversion into formic acid

Electrochemical reduction of CO2 (ECO2RR) to formate is one of effective approaches to achieve carbon recycling processes. Despite Bi nanosheets (NSs) have been proven to be highly selective in ECO2RR to formate, the understanding of the true active sites is needed to further dig out the potential of catalytic activity of Bi NSs. In this work, we developed a rational synthesis approach to manipulate the basal-/edge-plane ratio of Bi NSs via topotactic reduction of (004)-oriented Bi5O7I NSs and (102)-oriented BiOI NSs to reveal the contribution of basal and edge planes on the performance of ECO2RR. In comparison with edge-oriented Bi NSs, basal-oriented Bi NSs show higher catalytic activity. DFT calculations have proven that the competition of the kinetically favored HER would be inhibited on basal planes of Bi NSs, indicating the increasement of the proportion of basal planes on Bi NSs or Bi based 2D catalysts improves ECO2RR conversion efficiency.

Unravelling the electrocatalytic activity of bismuth nanosheets towards carbon dioxide reduction: Edge plane versus basal plane

Electrocatalytic CO2 reduction reaction (CO2 RR) toward formate production can be operated under mild conditions with high energy conversion efficiency while migrating the greenhouse effect. Herein, an integrated 3D open network of interconnected bismuthene arrays (3D Bi-ene-A/CM) is fabricated via in situ electrochemically topotactic transformation from BiOCOOH nanosheet arrays supported on the copper mesh. The resulted 3D Bi-ene-A/CM consists of 2D atomically thin metallic bismuthene (Bi-ene) in the form of an integrated array superstructure with a 3D interconnected and open network, which harvests the multiple structural advantages of both metallenes and self-supported electrodes for electrocatalysis. Such distinctive superstructure affords the maximized quantity and availability of the active sites with high intrinsic activity and superior charge and mass transfer capability, endowing the catalyst with good CO2 RR performance for stable formate production with high Faradaic efficiency (≈90%) and current density (>300 mA cm-2 ). Theoretical calculation verifies the superior intermediate stabilization of the dominant Bi plane during CO2 RR. Moreover, by further coupling anodic methanol oxidation reaction, an exotic electrolytic system enables highly energy-efficient and value-added pair-electrosynthesis for concurrent formate production at both electrodes, achieving substantially improved electrochemical and economic efficiency and revealing the feasibility for practical implementation.

Integrated 3D Open Network of Interconnected Bismuthene Arrays for Energy-Efficient and Electrosynthesis-Assisted Electrocatalytic CO2 Reduction.

Bismuth nanosheets (BiNSs) have been recognized as a promising catalyst for electrochemical CO2 reduction (CO2RR) to formate, but their preparation typically involves an elaborate synthesis of Bi precursors under elevated temperatures and pressures. Here, we demonstrate a simple surfactant-free method of preparing Bi2O3-derived BiNSs (OD-BiNSs) by aqueous precipitation and cyclic voltammetry (CV) under ambient conditions. In situ morphology transformation from Bi2O3 to BiNSs was observed during CV, in which the presence of oxygen and the initial morphology of Bi2O3 are crucial for the phase transformation. The as-prepared OD-BiNSs showed 93% of faradic efficiency (FE) to formate with a partial current density of 62 mA cm-2 at -0.95 VRHE in the H-cell and >94% FE at 50-200 mA cm-2 with cell voltages of 2.4-4.0 V in the flow cell.

Bismuth Nanosheets Derived by In Situ Morphology Transformation of Bismuth Oxides for Selective Electrochemical CO2 Reduction to Formate.

We report an effective strategy to enhance CO2 electroreduction (CER) properties of Cu-based Ruddlesden-Popper (RP) perovskite oxides by engineering their A-site cation deficiencies. With La2-x CuO4-δ (L2-x C, x=0, 0.1, 0.2, and 0.3) as proof-of-concept catalysts, we demonstrate that their CER activity and selectivity (to C2+ or CH4 ) show either a volcano-type or an inverted volcano-type dependence on the x values, with the extreme point at x=0.1. Among them, at -1.4 V, the L1.9 C delivers the optimal activity (51.3 mA cm-2 ) and selectivity (41.5 %) for C2+ , comparable to or better than those of most reported Cu-based oxides, while the L1.7 C exhibits the best activity (25.1 mA cm-2 ) and selectivity (22.1 %) for CH4 . Such optimized CER properties could be ascribed to the favorable merits brought by the cation-deficiency-induced oxygen vacancies and/or CuO/RP hybrids, including the facilitated adsorption/activation of key reaction species and thus the manipulated reaction pathways.

Cation-Deficiency-Dependent CO2 Electroreduction over Copper-Based Ruddlesden-Popper Perovskite Oxides.

2D bismuth nanosheets are a promising layered material for formate-producing via electrocatalytic CO2 conversion. However, the commercial interest of bismuth nanosheets in CO2 electroreduction is still rare due to the undesirable current density for formate at moderate operation potentials (about 200 mA mg-1 ) and harsh synthesis conditions (high temperature and/or high pressure). This work reports the preparation of Bi nanosheets with a lateral size in micrometer-scale via electrochemical cathodic exfoliation in aqueous solution at normal pressure and temperature. As-prepared Bi LNSs (L indicates large lateral size) possess high Faradaic efficiencies over 90% within a broad potential window from -0.44 to -1.10 V versus RHE and a superior partial current density about 590 mA mg-1 for formate in comparison with state-of-the-art results. Structure analysis, electrochemical results, and density functional theory calculations demonstrate that the increasing tensile lattice strain observed in Bi LNSs leads to less overlap of d orbitals and a narrower d-band width, which tuning the intermediate binding energies, and therefore promotes the intrinsic activity.

CO2 Electroreduction to Formate at a Partial Current Density up to 590 mA mg−1 via Micrometer-Scale Lateral Structuring of Bismuth Nanosheets

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Unravelling the electrocatalytic activity of bismuth nanosheets towards carbon dioxide reduction: Edge plane versus basal plane

CO2 Electroreduction to Formate at a Partial Current Density up to 590 mA mg−1 via Micrometer-Scale Lateral Structuring of Bismuth Nanosheets