Improving the electrocatalytic CO2 to formate conversion on bismuth using polyaniline as an electron pump

doi:10.1016/S1872-2067(25)64833-9

Abstract

Abstract:

Bi-based catalysts are known to promote the electrochemical reduction of CO₂to formic acid (HCOOH) or formate (HCOO^-). However, their implementation presents challenges: the first H⁺/e^- pair transfer to form the key *OCHO intermediate on a Bi surface is a slow, kinetically sluggish endergonic process, resulting in a large overpotential and narrow potential window for high HCOOH/HCOO^- selectivity. Altering the localized p-orbital electron states of Bi to change intermediate binding behaviors is difficult. We addressed this problem by using an in-situ polymerization method to obtain a polyaniline-Bi hybrid (PANI-Bi) with Bi surrounded by PANI chains. Combined experimental and computational studies indicate that the polyaniline acted as an “electron pump” that facilitated charge transfer from the PANI backbone to the Bi surface and changed the p-orbital electrons of the Bi active sites. This lowered the energy barrier for the adsorption of intermediates and facilitated *OCHO formation. Consequently, a significant increase in formate production was observed, achieving a single-pass carbon efficiency exceeding 48.7% at 800 mA cm^-2. This organic functionalization strategy, aimed at modifying the electronic structure of heterogeneous catalysts, offers a promising approach for achieving highly selective electroreduction of CO₂ at a high current density.

Key words: CO₂ reduction, Electrocatalysis, Bi-based catalyst, Polyaniline, Electron pump

Juxia Xiong, Hao Ma, Yingjun Dong, Benjamin Liu, Xiangji Zhou, Linbo Li, Yuanmiao Sun, Xiaolong Zhang, Hui-Ming Cheng. Improving the electrocatalytic CO₂ to formate conversion on bismuth using polyaniline as an electron pump[J]. Chinese Journal of Catalysis, 2026, 80: 237-247.

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URL: https://www.cjcatal.com/EN/10.1016/S1872-2067(25)64833-9

https://www.cjcatal.com/EN/Y2026/V80/I1/237

Figures/Tables 4

Fig. 1. Synthesis and structural characterization of PANI-Bi: (a) Schematic of PANI-Bi synthesis (“Substrate” = PTFE carbon, gray = C, white = H, blue = N, white = Bi). (b) Cross-sectional SEM image of PANI-Bi. SEM images of upper PANI-Bi catalyst layer (c) and PTFE carbon (d). (e) Cross-sectional image and corresponding EDS elemental maps of Bi, N, and C. (f) SEM surface scanning line diagrams of Bi, N, and C. (g, h) representative high-resolution TEM image of PANI-Bi. (i) Contact angle measurements of PANI-Bi. (j) Gas permeability of PTFE carbon, Bi, and PANI-Bi electrodes.

Fig. 2. Electronic structural and compositional characterization of Bi and PANI-Bi electrocatalyst before CO2 reduction. (a) XRD patterns. (b) FTIR of the Bi and PANI-Bi samples. (c) CO2 adsorption capacity from CO2-TPD data. XPS spectra of Bi 4f (d) and N 1s (e) for PANI-Bi and Bi catalysts. (f) Bi L-edge XANES spectra of PANI-Bi and a physically mixed PANI/Bi sample compared to Bi foil or Bi2O3 standards.

Fig. 3. CO2 electroreduction performance: FE of HCOO- (a) and H2 and CO (b) for Bi and PANI-Bi. Error bars represent standard deviations of three measurements. (c) Comparison of FE as a function of formate current density with catalysts reported in literature (Table S2). (d) Long-term operation of reduction device for pure HCOO- solution production at ?0.57 V. PANI-Bi catalyst displays impressive stability over 75 h at 200 mA cm?2 average current density. Comparison of CO2RR performances for a PANI-Bi catalyst on conventional carbon paper and PTFE carbon: schematic of CO2 distributions in conventional carbon paper (e) and PTFE carbon (f). (g) Single-pass conversion efficiencies of CO2R to HCOO- with PANI-Bi hybrid on PTFE carbon and carbon paper, respectively, at 800 mA cm?2 using different CO2 flow rates.

Fig. 4. Results of DFT calculations and proposed mechanism. (a) Structural model of Bi (012) surface and PANI-Bi (012) surface. (b) Free energy diagram for CO2RR on Bi (012) and PANI-Bi (012) surfaces; red lines represent corresponding rate-determining steps. (c) Free energy diagram for HER on Bi (012) and PANI-Bi (012) surfaces. (d) Comparison of adsorption energy for adsorbed *COOH and *OCHO species on Bi (012) and PANI-Bi (012) surfaces. (e) Partial density of states for Bi (012) and PANI-Bi (012) surfaces; Fermi level is set to zero. (f) Charge density difference for PANI-Bi (012) surface (upper panel); cyan and yellow represent charge depletion and charge accumulation areas, respectively. Local density of states for Bi (012) and PANI-Bi (012) surfaces with adsorbed *OCHO species (bottom panel). (g) Expected reaction mechanism of formate and CO formation during CO2RR on the PANI-Bi (012) surface.

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Improving the electrocatalytic CO₂ to formate conversion on bismuth using polyaniline as an electron pump

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