Efficient CO2-to-methanol electrocatalysis in acidic media via microenvironment-tuned cobalt phthalocyanine

Yun Song; Charles B. Musgrave III; Jianjun Su; Libei Huang; Weihua Guo; Yong Liu; Geng Li; Yinger Xin; Qiang Zhang; Xing Feng; Can Liao; Shunjie Liu; Ryan Tsz Kin Kwok; Jacky W. Y. Lam; Mingming He; Kai Shen Choong; Zhenxing Feng; Ben Zhong Tang; William A. Goddard III; Ruquan Ye

doi:10.1038/s41565-025-02059-z

Efficient CO₂-to-methanol electrocatalysis in acidic media via microenvironment-tuned cobalt phthalocyanine

Yun Song (Co-first Author)
, Charles B. Musgrave III (Co-first Author)
, Jianjun Su
, Libei Huang
, Weihua Guo
, Yong Liu
, Geng Li
, Yinger Xin
, Qiang Zhang
, Xing Feng
, Can Liao
, Shunjie Liu
, Ryan Tsz Kin Kwok
, Jacky W. Y. Lam
, Mingming He
, Kai Shen Choong
, Zhenxing Feng
, Ben Zhong Tang^*
, William A. Goddard III^*
, Ruquan Ye^*

^*Corresponding author for this work

Research output: Journal Publications and Reviews › RGC 21 - Publication in refereed journal › peer-review

26 Citations (Scopus)

Abstract

Electrosynthesis of value-added chemicals in strong acids can mitigate carbon loss and the operational cost of CO₂ reduction reaction (CO₂RR). However, molecular catalysis for CO₂RR is typically conducted in neutral or alkaline environments. CO₂RR in acidic media is challenged by the scarcity of catalyst candidates, competitive hydrogen evolution and slow product formation. Here we report a locally ionic yet simultaneously hydrophobic and aerophilic layered structure that modulates the microenvironment surrounding cobalt phthalocyanine (CoPc) molecular catalysts, enabling efficient, multielectron CO₂RR in acidic media. Experiment and theoretical modelling reveal that the polarized electrostatic field arising from the cationic groups suppresses hydronium migration. Concurrently, the van der Waals forces between the reactant gas and alkyl groups improve local CO availability, combining to achieve a methanol partial current density of 132 mA cm⁻² with 62% selectivity at a pH of ~1 and –1.37 V_RHE for CoPc, exceeding previous reports on neutral or alkaline electrolytes. The improved CO coverage also enables the detection of *CHO and *CO intermediates from in situ spectroscopy. We validate our strategy on various molecules, which champion the efficient inhibition of hydrogen evolution and improved CO₂RR partial current density in acidic media. CoPc-based layered structure with similar ionic, hydrophobic and aerophilic interfaces also yields comparable methanol productivity. © The Author(s), under exclusive licence to Springer Nature Limited 2025.

Original language	English
Pages (from-to)	78–86
Number of pages	12
Journal	Nature Nanotechnology
Volume	21
Issue number	1
Online published	17 Nov 2025
DOIs	https://doi.org/10.1038/s41565-025-02059-z
Publication status	Published - Jan 2026

Funding

R.Y. acknowledges support from the National Natural Science Foundation of China (22522509), Guangdong Basic and Applied Basic Research Fund (2024A1515030164), Hong Kong Research Grant Council (11310624, 11309723), the Shenzhen Science and Technology Program (JCYJ20220818101204009) and the State Key Laboratory of Marine Environmental Health (SKLMP/SCRF/0060). B.Z.T. acknowledges support from the National Key Research and Development Program of China (2023YFB381001), National Natural Science Fundation of China (52333007), Key-Area Research and Development Program of Guangdong Province (2024B0101040001), Shenzhen Key Laboratory of Functional Aggregate Materials (ZDSYS20211021111400001), the Science Technology Innovation Commission of Shenzhen Municipality (KQTD20210811090142053 and JCYJ20220818103007014) and the Innovation and Technology Commission (ITC-CNERC14SC01). X-ray absorption spectroscopy measurements were carried out at the Shanghai Synchrotron Radiation Facility of BL14W1 ( https://cstr.cn/31124.02.SSRF.BL14W1 ). C.B.M. III and W.A.G. III acknowledge support from the Liquid Sunlight Alliance, which is supported by the US Department of Energy, Office of Science, Office of Basic Energy Sciences, Fuels from Sunlight Hub, under award number DE-SC0021266. Z.F. acknowledges support from the China Experience Fund and the Stephen Slavens Faculty Scholar Endowment Fund from Oregon State University.

UN SDGs

This output contributes to the following UN Sustainable Development Goals (SDGs)

SDG 7 Affordable and Clean Energy
SDG 13 Climate Action

RGC Funding Information

RGC-funded

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Song, Y., Musgrave III, C. B., Su, J., Huang, L., Guo, W., Liu, Y., Li, G., Xin, Y., Zhang, Q., Feng, X., Liao, C., Liu, S., Kwok, R. T. K., Lam, J. W. Y., He, M., Choong, K. S., Feng, Z., Tang, B. Z., Goddard III, W. A., & Ye, R. (2026). Efficient CO₂-to-methanol electrocatalysis in acidic media via microenvironment-tuned cobalt phthalocyanine. Nature Nanotechnology, 21(1), 78–86. https://doi.org/10.1038/s41565-025-02059-z

@article{9b13e4b92b7640cf997f08296227abe2,

title = "Efficient CO2-to-methanol electrocatalysis in acidic media via microenvironment-tuned cobalt phthalocyanine",

abstract = "Electrosynthesis of value-added chemicals in strong acids can mitigate carbon loss and the operational cost of CO2 reduction reaction (CO2RR). However, molecular catalysis for CO2RR is typically conducted in neutral or alkaline environments. CO2RR in acidic media is challenged by the scarcity of catalyst candidates, competitive hydrogen evolution and slow product formation. Here we report a locally ionic yet simultaneously hydrophobic and aerophilic layered structure that modulates the microenvironment surrounding cobalt phthalocyanine (CoPc) molecular catalysts, enabling efficient, multielectron CO2RR in acidic media. Experiment and theoretical modelling reveal that the polarized electrostatic field arising from the cationic groups suppresses hydronium migration. Concurrently, the van der Waals forces between the reactant gas and alkyl groups improve local CO availability, combining to achieve a methanol partial current density of 132 mA cm−2 with 62\% selectivity at a pH of \textasciitilde{}1 and –1.37 VRHE for CoPc, exceeding previous reports on neutral or alkaline electrolytes. The improved CO coverage also enables the detection of *CHO and *CO intermediates from in situ spectroscopy. We validate our strategy on various molecules, which champion the efficient inhibition of hydrogen evolution and improved CO2RR partial current density in acidic media. CoPc-based layered structure with similar ionic, hydrophobic and aerophilic interfaces also yields comparable methanol productivity. {\textcopyright} The Author(s), under exclusive licence to Springer Nature Limited 2025.",

author = "Yun Song and \{Musgrave III\}, \{Charles B.\} and Jianjun Su and Libei Huang and Weihua Guo and Yong Liu and Geng Li and Yinger Xin and Qiang Zhang and Xing Feng and Can Liao and Shunjie Liu and Kwok, \{Ryan Tsz Kin\} and Lam, \{Jacky W. Y.\} and Mingming He and Choong, \{Kai Shen\} and Zhenxing Feng and Tang, \{Ben Zhong\} and \{Goddard III\}, \{William A.\} and Ruquan Ye",

year = "2026",

month = jan,

doi = "10.1038/s41565-025-02059-z",

language = "English",

volume = "21",

pages = "78–86",

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Song, Y, Musgrave III, CB, Su, J , Huang, L , Guo, W , Liu, Y , Li, G , Xin, Y , Zhang, Q, Feng, X, Liao, C, Liu, S, Kwok, RTK, Lam, JWY, He, M, Choong, KS, Feng, Z, Tang, BZ, Goddard III, WA & Ye, R 2026, 'Efficient CO₂-to-methanol electrocatalysis in acidic media via microenvironment-tuned cobalt phthalocyanine', Nature Nanotechnology, vol. 21, no. 1, pp. 78–86. https://doi.org/10.1038/s41565-025-02059-z

Efficient CO₂-to-methanol electrocatalysis in acidic media via microenvironment-tuned cobalt phthalocyanine. / Song, Yun (Co-first Author); Musgrave III, Charles B. (Co-first Author); Su, Jianjun et al.
In: Nature Nanotechnology, Vol. 21, No. 1, 01.2026, p. 78–86.

Research output: Journal Publications and Reviews › RGC 21 - Publication in refereed journal › peer-review

TY - JOUR

T1 - Efficient CO2-to-methanol electrocatalysis in acidic media via microenvironment-tuned cobalt phthalocyanine

AU - Song, Yun

AU - Musgrave III, Charles B.

AU - Su, Jianjun

AU - Huang, Libei

AU - Guo, Weihua

AU - Liu, Yong

AU - Li, Geng

AU - Xin, Yinger

AU - Zhang, Qiang

AU - Feng, Xing

AU - Liao, Can

AU - Liu, Shunjie

AU - Kwok, Ryan Tsz Kin

AU - Lam, Jacky W. Y.

AU - He, Mingming

AU - Choong, Kai Shen

AU - Feng, Zhenxing

AU - Tang, Ben Zhong

AU - Goddard III, William A.

AU - Ye, Ruquan

PY - 2026/1

Y1 - 2026/1

N2 - Electrosynthesis of value-added chemicals in strong acids can mitigate carbon loss and the operational cost of CO2 reduction reaction (CO2RR). However, molecular catalysis for CO2RR is typically conducted in neutral or alkaline environments. CO2RR in acidic media is challenged by the scarcity of catalyst candidates, competitive hydrogen evolution and slow product formation. Here we report a locally ionic yet simultaneously hydrophobic and aerophilic layered structure that modulates the microenvironment surrounding cobalt phthalocyanine (CoPc) molecular catalysts, enabling efficient, multielectron CO2RR in acidic media. Experiment and theoretical modelling reveal that the polarized electrostatic field arising from the cationic groups suppresses hydronium migration. Concurrently, the van der Waals forces between the reactant gas and alkyl groups improve local CO availability, combining to achieve a methanol partial current density of 132 mA cm−2 with 62% selectivity at a pH of ~1 and –1.37 VRHE for CoPc, exceeding previous reports on neutral or alkaline electrolytes. The improved CO coverage also enables the detection of *CHO and *CO intermediates from in situ spectroscopy. We validate our strategy on various molecules, which champion the efficient inhibition of hydrogen evolution and improved CO2RR partial current density in acidic media. CoPc-based layered structure with similar ionic, hydrophobic and aerophilic interfaces also yields comparable methanol productivity. © The Author(s), under exclusive licence to Springer Nature Limited 2025.

AB - Electrosynthesis of value-added chemicals in strong acids can mitigate carbon loss and the operational cost of CO2 reduction reaction (CO2RR). However, molecular catalysis for CO2RR is typically conducted in neutral or alkaline environments. CO2RR in acidic media is challenged by the scarcity of catalyst candidates, competitive hydrogen evolution and slow product formation. Here we report a locally ionic yet simultaneously hydrophobic and aerophilic layered structure that modulates the microenvironment surrounding cobalt phthalocyanine (CoPc) molecular catalysts, enabling efficient, multielectron CO2RR in acidic media. Experiment and theoretical modelling reveal that the polarized electrostatic field arising from the cationic groups suppresses hydronium migration. Concurrently, the van der Waals forces between the reactant gas and alkyl groups improve local CO availability, combining to achieve a methanol partial current density of 132 mA cm−2 with 62% selectivity at a pH of ~1 and –1.37 VRHE for CoPc, exceeding previous reports on neutral or alkaline electrolytes. The improved CO coverage also enables the detection of *CHO and *CO intermediates from in situ spectroscopy. We validate our strategy on various molecules, which champion the efficient inhibition of hydrogen evolution and improved CO2RR partial current density in acidic media. CoPc-based layered structure with similar ionic, hydrophobic and aerophilic interfaces also yields comparable methanol productivity. © The Author(s), under exclusive licence to Springer Nature Limited 2025.

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U2 - 10.1038/s41565-025-02059-z

DO - 10.1038/s41565-025-02059-z

M3 - RGC 21 - Publication in refereed journal

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JO - Nature Nanotechnology

JF - Nature Nanotechnology

IS - 1

ER -

Efficient CO₂-to-methanol electrocatalysis in acidic media via microenvironment-tuned cobalt phthalocyanine

Abstract

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GRF: Designing Effective Molecule/Electrode Interfaces for Universal Molecular CO2 Reduction in Strong Acids

GRF: Steering the Local Environment of Ultrathin Covalent Organic Polymers for Efficient Electroreduction of CO2 to Methanol

Cite this

Efficient CO2-to-methanol electrocatalysis in acidic media via microenvironment-tuned cobalt phthalocyanine

Abstract

Funding

UN SDGs

RGC Funding Information

Access Output

Other Access Options

Permanent Link

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Projects

GRF: Designing Effective Molecule/Electrode Interfaces for Universal Molecular CO2 Reduction in Strong Acids

GRF: Steering the Local Environment of Ultrathin Covalent Organic Polymers for Efficient Electroreduction of CO2 to Methanol

Cite this

Efficient CO₂-to-methanol electrocatalysis in acidic media via microenvironment-tuned cobalt phthalocyanine