Copper nanoclusters derived from copper phthalocyanine as real active sites for CO₂ electroreduction: Exploring size dependency on selectivity-A mini review

Abstract

The electrochemical reduction reaction of CO₂ (CO₂RR) holds promise for converting CO₂ into valuable fuels and chemicals, particularly when powered by renewable electricity, thereby aiding in reducing atmospheric CO₂ levels and addressing climate change. Copper phthalocyanine and its derivatives (Cu-Pcs) have attracted significant attention as versatile electrocatalytic materials with high selectivity toward various hydrocarbon products. However, the real active sites of Cu-Pcs for different products vary, and there is a lack of comprehensive summary. To address this gap, we analyze and summarize previous research, yielding the following insights: Cu-Pcs undergo reconstruction and demetallization during CO₂RR, with Cu(II) converting to Cu₍₀₎, forming transient copper nanoclusters (Cu NCs). The selectivity for CO₂RR products closely correlates with the size of those derived Cu NCs. Specifically, reversible Cu NCs with ultrasmall sizes (≤2 nm), which revert to Cu-Pcs after electrolysis, exhibit high selectivity toward CH₄. As Cu NCs increase in size, there is a higher CO coverage, promoting CO generation. When Cu NCs exceed a critical threshold size (approximately 15 nm), C-C coupling can occur, facilitating the formation of multicarbon (C₂₊) products. Furthermore, the structure of macrocycles, types of functional groups, and properties of carbon substrates influence the size and electron density of Cu NCs, thereby impacting the selectivity of CO₂RR products.

Keywords

CO ₂ reduction reaction / copper phthalocyanine / Cu nanoclusters / real active sites

References

[1] Peplow M. The race to upcycle CO₂ into fuels, concrete and more. Nature. 2022;603(7903):780-783.

[2] De Luna P, Hahn C, Higgins D, Jaffer SA, Jaramillo TF, Sargent EH. What would it take for renewably powered electrosynthesis to displace petrochemical processes? Science. 2019;364(6438):1-9.

[3] Jones JP, Prakash GKS, Olah GA. Electrochemical CO₂ reduction: recent advances and current trends. Isr J Chem. 2014;54(10):1451-1466.

[4] Li Y, Sun Q. Recent advances in breaking scaling relations for effective electrochemical conversion of CO₂. Adv Energy Mater. 2016;6(17):1-9.

[5] Wu Y, Jiang Z, Lu X, Liang Y, Wang H. Domino electroreduction of CO₂ to methanol on a molecular catalyst. Nature. 2019;575(7784):639-642.

[6] She ZW, Kibsgaard J, Dickens CF, Chorkendorff I, Nørskov JK, Jaramillo TF. Combining theory and experiment in electrocatalysis: insights into materials design. Science. 2017;355:1-12.

[7] Yue Z, Ou C, Ding N, Tao L, Zhao J, Chen J. Advances in metal phthalocyanine based carbon composites for electrocatalytic CO₂ reduction. ChemCatChem. 2020;12(24):6103-6130.

[8] Liu W, Zhai P, Li A, et al. Electrochemical CO₂ reduction to ethylene by ultrathin CuO nanoplate arrays. Nat Commun. 2022;13:1-12.

[9] Wang H, Tzeng YK, Ji Y, et al. Synergistic enhancement of electrocatalytic CO₂ reduction to C₂ oxygenates at nitrogen-doped nanodiamonds/Cu interface. Nat Nanotechnol. 2020;15(2):131-137.

[10] Liu T, Ohashi K, Nagita K, Harada T, Nakanishi S, Kamiya K. A tin oxide-coated copper foam hybridized with a gas diffusion electrode for efficient CO₂ reduction to formate with a current density exceeding 1 A cm⁻². Small. 2022;18(50):2205323.

[11] Hu L, Wrubel JA, Baez-Cotto CM, et al. A scalable membrane electrode assembly architecture for efficient electrochemical conversion of CO₂ to formic acid. Nat Commun. 2023;14:1-11.

[12] Ou H, Wang D, Li Y. How to select effective electrocatalysts: nano or single atom? Nano Sel. 2021;2(3):492-511.

[13] Liu A, Liu L, Cao Y, et al. Controlling dynamic structural transformation of atomically dispersed CuO_x species and influence on their catalytic performances. ACS Catal. 2019;9(11):9840-9851.

[14] Yang Y, Louisia S, Yu S, et al. Operando studies reveal active Cu nanograins for CO₂ electroreduction. Nature. 2023;614(7947):262-269.

[15] Gu X, Jiao Y, Wei B, et al. Boron bridged NiN4B2Cx single-atom catalyst for superior electrochemical CO₂ reduction. Mater Today. 2022;54:63-71.

[16] Cai Y, Fu J, Zhou Y, et al. Insights on forming N, O-coordinated Cu single-atom catalysts for electrochemical reduction CO₂ to methane. Nat Commun. 2021;12:1-9.

[17] Liu C, Da Zhang X, Huang JM, Guan MX, Xu M, Gu ZY. In situ reconstruction of Cu–N coordinated MOFs to generate dispersive Cu/Cu2O nanoclusters for selective electroreduction of CO₂ to C₂H₄. ACS Catal. 2022;12(24):15230-15240.

[18] Li J, Zitolo A, Garcés-Pineda FA, et al. Metal oxide clusters on nitrogen-doped carbon are highly selective for CO₂ electroreduction to CO. ACS Catal. 2021;11(15):10028-10042.

[19] Creissen CE, Fontecave M. Keeping sight of copper in single-atom catalysts for electrochemical carbon dioxide reduction. Nat Commun. 2022;13:1-4.

[20] Zhang Y, Zhang X, Jiao L, Meng Z, Jiang HL. Conductive covalent organic frameworks of polymetallophthalocyanines as a tunable platform for electrocatalysis. J Am Chem Soc. 2023;145(44):24230-24239.

[21] Chang Q, Liu Y, Lee JH, et al. Metal-coordinated phthalocyanines as platform molecules for understanding isolated metal sites in the electrochemical reduction of CO₂. J Am Chem Soc. 2022;144(35):16131-16138.

[22] Yang S, Yu Y, Gao X, Zhang Z, Wang F. Recent advances in electrocatalysis with phthalocyanines. Chem Soc Rev. 2021;50(23):12985-13011.

[23] Kumar A, Kumar Vashistha V, Kumar Das D. Recent development on metal phthalocyanines based materials for energy conversion and storage applications. Coord Chem Rev. 2021;431:1-19.

[24] Sorokin AB. Phthalocyanine metal complexes in catalysis. Chem. Rev. 2013;113(10):8152-8191.

[25] Wu Y, Liang Y, Wang H. Heterogeneous molecular catalysts of metal phthalocyanines for electrochemical CO₂ reduction reactions. Acc Chem Res. 2021;54(16):3149-3159.

[26] Hadimani S, Aralekallu S, Sannegowda LK. Tuning palladium(II) phthalocyanine embedded hybrid electrocatalyst for hydrogen evolution reaction. Sustain Energy Fuels. 2024;1:1-13.

[27] Monama GR, Modibane KD, Ramohlola KE, et al. Copper(II) phthalocyanine/metal organic framework electrocatalyst for hydrogen evolution reaction application. Int J Hydrogen Energy. 2019;44(34):18891-18902.

[28] Qi D, Chen X, Liu W, et al. A Ni/Fe-based heterometallic phthalocyanine conjugated polymer for the oxygen evolution reaction. Inorg Chem Front. 2020;7(3):642-646.

[29] Aralekallu S, Sajjan VA, Palanna M, Prabhu C P K, Hojamberdiev M, Sannegowda LK. Ni foam-supported azo linkage cobalt phthalocyanine as an efficient electrocatalyst for oxygen evolution reaction. J Power Sources. 2020;449:227516.

[30] Huang H, Lan Z, Li W, Mo W, Zhao L, Zhang J. A novel and low-cost CuPc@C catalyst derived from the compounds of sunflower straw and copper phthalocyanine pigment for oxygen reduction reaction. RSC Adv. 2021;11(26):15590-15597.

[31] Yabu H, Nakamura K, Matsuo Y, et al. Pyrolysis-free oxygen reduction reaction (ORR) electrocatalysts composed of unimolecular layer metal azaphthalocyanines adsorbed onto carbon materials. ACS Appl Energy Mater. 2021;4(12):14380-14389.

[32] Ishibashi K, Ito K, Yabu H. Rare-metal-free Zn–air batteries with ultrahigh voltage and high power density achieved by iron azaphthalocyanine unimolecular layer (AZUL) electrocatalysts and acid/alkaline tandem aqueous electrolyte cells. APL Energy. 2023;1:016106.

[33] Abe H, Hirai Y, Ikeda S, et al. Fe azaphthalocyanine unimolecular layers (Fe AzULs) on carbon nanotubes for realizing highly active oxygen reduction reaction (ORR) catalytic electrodes. NPG Asia Mater. 2019;11:1-12.

[34] Furuya N, Koide S. Electroreduction of carbon dioxide by metal phthalocyanines. Electrochim Acta. 1991;36(8):1309-1313.

[35] Zhang X, Wang Y, Gu M, et al. Molecular engineering of dispersed nickel phthalocyanines on carbon nanotubes for selective CO₂ reduction. Nat Energy. 2020;5(9):684-692.

[36] Feng Q, Sun Y, Gu X, Dong Z. Advances of cobalt phthalocyanine in electrocatalytic CO₂ reduction to CO: a mini review. Electrocatalysis. 2022;13(6):675-690.

[37] Zhang X, Wu Z, Zhang X, et al. Highly selective and active CO₂ reduction electrocatalysts based on cobalt phthalocyanine/carbon nanotube hybrid structures. Nat Commun. 2017;8:1-8.

[38] Karapinar D, Zitolo A, Huan TN, et al. Carbon-nanotube-supported copper polyphthalocyanine for efficient and selective electrocatalytic CO₂ reduction to CO. ChemSusChem. 2020;13(1):173-179.

[39] Guan A, Chen Z, Quan Y, et al. Boosting CO₂ electroreduction to CH₄ via tuning neighboring single-copper sites. ACS Energy Lett. 2020;5(4):1044-1053.

[40] Zhang H, Yang Y, Liang Y, et al. Molecular stabilization of sub-nanometer Cu clusters for selective CO₂ electromethanation. ChemSusChem. 2022;15:1-7.

[41] Weng Z, Wu Y, Wang M, et al. Active sites of copper-complex catalytic materials for electrochemical carbon dioxide reduction. Nat Commun. 2018;9:1-9.

[42] Zhang J, My Pham TH, Gao Z, et al. Electrochemical CO₂ reduction over copper phthalocyanine derived catalysts with enhanced selectivity for multicarbon products. ACS Catal. 2023;13(14):9326-9335.

[43] Xu Y, Li F, Xu A, et al. Low coordination number copper catalysts for electrochemical CO₂ methanation in a membrane electrode assembly. Nat Commun. 2021;12:4-10.

[44] Xu F, Wang Z, Liu Z, et al. Coordination environment engineering of transition metal doped phthalocyanine single-atom catalysts for carbon dioxide reduction reaction: a DFT study. Mol Catal. 2023;550:113617.

[45] Kusama S, Saito T, Hashiba H, Sakai A, Yotsuhashi S. Crystalline copper(II) phthalocyanine catalysts for electrochemical reduction of carbon dioxide in aqueous media. ACS Catal. 2017;7(12):8382-8385.

[46] Latiff NM, Fu X, Mohamed DK, Veksha A, Handayani M, Lisak G. Carbon based copper(II) phthalocyanine catalysts for electrochemical CO₂ reduction: effect of carbon support on electrocatalytic activity. Carbon N. Y. 2020;168:245-253.

[47] Mei B, Liu C, Li J, et al. Operando HERFD-XANES and surface sensitive Δµ analyses identify the structural evolution of copper(II) phthalocyanine for electroreduction of CO₂. J Energy Chem. 2022;64:1-7.

[48] Boutin E, Salamé A, Robert M. Confined molecular catalysts provide an alternative interpretation to the electrochemically reversible demetallation of copper complexes. Nat Commun. 2022;13:11-13.

[49] Weng Z, Wu Y, Wang M, et al. Reply To: confined molecular catalysts provide an alternative interpretation to the electrochemically reversible demetallation of copper complexes. Nat Commun. 2022;13:6-8.

[50] Reske R, Mistry H, Behafarid F, Roldan Cuenya B, Strasser P. Particle size effects in the catalytic electroreduction of CO₂ on Cu nanoparticles. J Am Chem Soc. 2014;136:6978-6989.

[51] Qiu XF, Zhu HL, Huang JR, Liao PQ, Chen XM. Highly selective CO₂ electroreduction to C₂H₄ using a metal–organic framework with dual active sites. J Am Chem Soc. 2021;143(19):7242-7246.

[52] Ma L, Hu W, Mei B, et al. Covalent triazine framework confined copper catalysts for selective electrochemical CO₂ reduction: operando diagnosis of active sites. ACS Catal. 2020;10:4534-4542.

[53] Rong W, Zou H, Zang W, et al. Size-dependent activity and selectivity of atomic-level copper nanoclusters during CO/CO₂ electroreduction. Angew Chem Int Ed. 2021;60:466-472.

[54] Karapinar D, Huan NT, Ranjbar Sahraie N, et al. Electroreduction of CO₂ on single-site copper-nitrogen-doped carbon material: selective formation of ethanol and reversible restructuration of the metal sites. Angew Chem Int Ed. 2019;58:15098-15103.

[55] Ruocco A, Evangelista F, Gotter R, Attili A, Stefani G. Evidence of charge transfer at the Cu-phthalocyanine/Al(100) interface. J Phys Chem C. 2008;112:2016-2025.

RIGHTS & PERMISSIONS

2024 The Author(s). EcoEnergy published by John Wiley & Sons Australia, Ltd on behalf of China Chemical Safety Association.