Metal Oxide/Nitrogen-Doped Carbon Catalysts Enables Highly Efficient CO₂ Electroreduction

Abstract

The metal oxide/nitrogen-doped carbon (NC) compounds zirconium oxide/NC (ZrO₂/NC) and cerium oxide/NC (CeO₂/NC) were synthesized via the pyrolysis of polyaniline on the metal oxide surface. The characterization of the ZrO₂/NC and CeO₂/NC catalysts showed more active CO₂ reduction reaction activity than that of NC catalyst without metal oxide. Gas chromatography analysis revealed that CO and H₂ were the primary products, and no liquid-phase products were detected via proton nuclear magnetic resonance spectroscopy or high-performance liquid chromatography. The maximum Faraday efficiency of ZrO₂/NC reached 90% at − 0.73 V (vs. RHE), with the current density of CO at 5.5 mA/cm²; this Faraday efficiency value was higher than that of NC (41%), with the current density of CO at 3.1 mA/cm². The interaction between the metal oxide and carbon allowed the efficient formation of defect sites, especially imine-type nitrogen, strengthening the adsorption of the key reaction intermediate CO₂ ^•− and thus promoting the CO₂ reduction reaction.

Keywords

Metal oxide / Nitrogen-doped carbon / Interface effect / CO₂ reduction reaction

References

[1] Yan CC, Li HB, Ye YF, et al. Coordinatively unsaturated nickel–nitrogen sites towards selective and high-rate CO₂ electroreduction. Energy Environ Sci, 2018, 11(5): 1204-1210.

[2] Zhu DD, Liu JL, Qiao SZ Recent advances in inorganic heterogeneous electrocatalysts for reduction of carbon dioxide. Adv Mater, 2016, 28(18): 3423-3452.

[3] Hamann TW, Jensen RA, Martinson ABF, et al. Advancing beyond current generation dye-sensitized solar cells. Energy Environ Sci, 2008, 1(1): 66.

[4] He X, Qiu LQ, Wang WJ, et al. Photocarboxylation with CO₂: an appealing and sustainable strategy for CO₂ fixation. Green Chem, 2020, 22(21): 7301-7320.

[5] Li JS, Tian Y, Zhou YN, et al. Abiotic-biological hybrid systems for CO₂ conversion to value-added chemicals and fuels. Trans Tianjin Univ, 2020, 26(4): 237-247.

[6] Chang Q, Kim J, Lee JH, et al. Boosting activity and selectivity of CO₂ electroreduction by pre-hydridizing Pd nanocubes. Small, 2020, 16(49): 2005305.

[7] Xie H, Wan YY, Wang XM, et al. Boosting Pd-catalysis for electrochemical CO₂ reduction to CO on Bi-Pd single atom alloy nanodendrites. Appl Catal B Environ, 2021, 289: 119783.

[8] Ma C, Hou PF, Wang XP, et al. Carbon nanotubes with rich pyridinic nitrogen for gas phase CO₂ electroreduction. Appl Catal B Environ, 2019, 250: 347-354.

[9] Hou PF, Song WL, Wang XP, et al. Well-defined single-atom cobalt catalyst for electrocatalytic flue gas CO₂ reduction. Small, 2020, 16(24): 2001896.

[10] Yadav A, Kumar H, Sharma R, et al. Influence of polyaniline on the photocatalytic properties of metal nanocomposites: a review. Colloid Interface Sci, 2021, 40: 100339.

[11] Mohamad AIZ, Wadi HS, Gan SN, et al. Polyaniline (PAni) optical sensor in chloroform detection. Sensor Actuat B Chem, 2018, 261: 97-105.

[12] Li YQ, Mao YL, Xiao C, et al. Flexible pH sensor based on a conductive PANI membrane for pH monitoring. RSC Adv, 2020, 10(1): 21-28.

[13] Ahmad AL, Farooqui UR, Hamid NA Porous (PVDF-HFP/PANI/GO) ternary hybrid polymer electrolyte membranes for lithium-ion batteries. RSC Adv, 2018, 8(45): 25725-25733.

[14] Li LM, Liu EH, Shen HJ, et al. Charge storage performance of doped carbons prepared from polyaniline for supercapacitors. J Solid State Electrochem, 2011, 15(1): 175-182.

[15] Yan J, Wei T, Qiao WM, et al. A high-performance carbon derived from polyaniline for supercapacitors. Electrochem Commun, 2010, 12(10): 1279-1282.

[16] Yin YL, Gao Y, Zhang YL, et al. Synthesis of honeycomb-like hierarchical porous carbon via molten salt pyrolysis in a novel sequencing integration system for high-performance supercapacitors. Microporous Mesoporous Mater, 2019, 278: 195-205.

[17] Taheri NN, Ramezanzadeh B, Mahdavian M Application of layer-by-layer assembled graphene oxide nanosheets/polyaniline/zinc cations for construction of an effective epoxy coating anti-corrosion system. J Alloy Compd, 2019, 800: 532-549.

[18] Li F, Li GX, Zeng J, et al. Molybdate-doped copolymer coatings for corrosion prevention of stainless steel. J Appl Polym Sci, 2014, 131(16): 40602.

[19] Wang H, Jia J, Song PF, et al. Efficient electrocatalytic reduction of CO₂ by nitrogen-doped nanoporous carbon/carbon nanotube membranes: a step towards the electrochemical CO₂ refinery. Angew Chem, 2017, 129(27): 7955-7960.

[20] Trchová M, Stejskal J Polyaniline: the infrared spectroscopy of conducting polymer nanotubes (IUPAC Technical Report). Pure Appl Chem, 2011, 83(10): 1803-1817.

[21] Kim JH, Woo H, Choi J, et al. CO₂ electroreduction on Au/TiC: enhanced activity due to metal–support interaction. ACS Catal, 2017, 7(3): 2101-2106.

[22] Han H, Jin S, Park S, et al. Plasma-induced oxygen vacancies in amorphous MnO _x boost catalytic performance for electrochemical CO₂ reduction. Nano Energy, 2021, 79: 105492.

[23] Yuan LP, Jiang WJ, Liu XL, et al. Molecularly engineered strong metal oxide–support interaction enables highly efficient and stable CO₂ electroreduction. ACS Catal, 2020, 10(22): 13227-13235.

[24] Hao LD, Sun ZY Metal oxide-based materials for electrochemical CO₂ reduction. Acta Phys Chimica Sin, 2021, 37(7): 2009033.

[25] Tauster SJ, Fung SC, Garten RL Strong metal-support interactions. Group 8 noble metals supported on titanium dioxide. J Am Chem Soc, 1978, 100(1): 170-175.

[26] Tauster SJ Strong metal-support interactions. Acc Chem Res, 1987, 20(11): 389-394.

[27] Tao HC, Choi C, Ding LX, et al. Nitrogen fixation by Ru single-atom electrocatalytic reduction. Chem, 2019, 5(1): 204-214.

[28] Han ZS, Choi C, Tao HC, et al. Tuning the Pd-catalyzed electroreduction of CO₂–CO with reduced overpotential. Catal Sci Technol, 2018, 8(15): 3894-3900.

[29] Kumar B, Asadi M, Pisasale D, et al. Renewable and metal-free carbon nanofibre catalysts for carbon dioxide reduction. Nat Commun, 2013, 4: 2819.

[30] Wu JJ, Sharifi T, Gao Y, et al. Emerging carbon-based heterogeneous catalysts for electrochemical reduction of carbon dioxide into value-added chemicals. Adv Mater, 2019, 31(13): 1804257.

[31] Chu J, Li X, Li QQ, et al. Hydrothermal synthesis of PANI nanowires for high-performance supercapacitor. High Perform Polym, 2020, 32(3): 258-267.

[32] de Castro SI, Sigoli FA, Mazali IO Reversible oxygen vacancy generation on pure CeO₂ nanorods evaluated by in situ Raman spectroscopy. J Phys Chem C, 2017, 121(23): 12928-12935.

[33] Villa-Aleman E, Houk AL, Dick DD, et al. Hyper-Raman spectroscopy of CeO₂. J Raman Spectrosc, 2020, 51(7): 1260-1263.

[34] Ji P, Wang Z, Shang XH, et al. Direct observation of enhanced Raman scattering on nano-sized ZrO₂ substrate: charge-transfer contribution. Front Chem, 2019, 7: 245.

[35] Silge A, Bocklitz T, Ossig R, et al. The interaction of an amino-modified ZrO₂ nanomaterial with macrophages–an in situ investigation by Raman microspectroscopy. Anal Bioanal Chem, 2016, 408(21): 5935-5943.

[36] Melánová K, Beneš L, Zima V, et al. Microcomposites of zirconium phosphonates with a conducting polymer, polyaniline: preparation, spectroscopic study and humidity sensing. J Solid State Chem, 2019, 276: 285-293.

[37] Rajagopal RV, Venkata PC Surface chemical states, electrical and carrier transport properties of Au/ZrO₂/n–GaN MIS junction with a high-k ZrO₂ as an insulating layer. Mater Sci Eng: B, 2018, 231: 74-80.

[38] Li WH, Nie XW, Jiang X, et al. ZrO₂ support imparts superior activity and stability of Co catalysts for CO₂ methanation. Appl Catal B Environ, 2018, 220: 397-408.

[39] Holgado JP, Alvarez R, Munuera G Study of CeO₂ XPS spectra by factor analysis: reduction of CeO₂. Appl Surf Sci, 2000, 161(3–4): 301-315.

[40] Yang CW, Bebensee F, Chen J, et al. Carbon dioxide adsorption on CeO₂(110): an XPS and NEXAFS study. ChemPhysChem, 2017, 18(14): 1874-1880.

[41] Zhang K, Zhang LL, Zhao XS, et al. Graphene/polyaniline nanofiber composites as supercapacitor electrodes. Chem Mater, 2010, 22(4): 1392-1401.

[42] Chen SH, Zhao XL, Xie FZ, et al. Efficient charge separation between ZnIn₂S₄ nanoparticles and polyaniline nanorods for nitrogen photofixation. New J Chem, 2020, 44(18): 7350-7356.