聚离子液体-富吡咯氮碳材料锚定痕量钯实现自优化CO2制DMC电催化过程

doi:10.1016/S1872-2067(26)65267-9

催化学报 ›› 2027, Vol. 92: 340-354.DOI: 10.1016/S1872-2067(26)65267-9

聚离子液体-富吡咯氮碳材料锚定痕量钯实现自优化CO₂制DMC电催化过程

李勇^a^,^b(), 刘一凡^b, 乔翠^b, 付梦倩^b, 杨子锋^b^,^*(), 李雨浓^b^,^*(), 张锁江^b^,^*()

^a 郑州大学化学学院, 河南郑州 450001
^b 中国科学院过程工程研究所, 固态电池及储能过程北京市重点实验室, 离子液体与低碳能源研究中心, 北京 100190

收稿日期:2026-04-09 接受日期:2026-06-17 出版日期:2027-01-02 发布日期:2026-10-30
通讯作者: *电子信箱: sjzhang@ipe.ac.cn (张锁江),
liyunong@ipe.ac.cn (李雨浓),
zfyang@ipe.ac.cn (杨子锋).
基金资助:
国家重点研发项目(2023YFA1507904);北京市自然科学基金(2242021);中国科学院战略性先导科技专项A类(XDA0390403);国家自然科学基金(U22A20416)

Poly(ionic liquid)-directed pyrrolic-N-rich carbon for trace-Pd anchoring toward self-optimizing CO₂-to-DMC electrocatalysis

Yong Li^a^,^b(), Yifan Liu^b, Cui Qiao^b, Mengqian Fu^b, Zifeng Yang^b^,^*(), Yunong Li^b^,^*(), Suojiang Zhang^b^,^*()

^a College of Chemistry, Zhengzhou University, Zhengzhou 450001, Henan, China
^b Center of Ionic Liquids and Green Energy, Beijing Key Laboratory of Solid-State Battery and Energy Storage Process, Institute of Process Engineering, Chinese Academy of Sciences, Beijing 100190, China

Received:2026-04-09 Accepted:2026-06-17 Online:2027-01-02 Published:2026-10-30
Contact: *E-mail: sjzhang@ipe.ac.cn (S. Zhang),
liyunong@ipe.ac.cn (Y. Li),
zfyang@ipe.ac.cn (Z. Yang).
About author:First author contact:Author contributions
Yong Li: Methodology, Validation, Formal analysis, Investigation, Data curation, Writing-original draft, Writing-review & editing, Visualization. Yifan Liu: Methodology, Formal analysis, Software. Cui Qiao: Investigation, Data curation. Mengqian Fu: Formal analysis, Methodology, Investigation. Zifeng Yang: Methodology, Supervision, Funding acquisition. Yunong Li: Conceptualization, Methodology, Data curation, Writing-review & editing, Resources, Funding Acquisition, Supervision. Suojiang Zhang: Visualization, Software, Project administration, Funding acquisition.
Supported by:
National Key Research and Development Program of China(2023YFA1507904);Beijing Natural Science Foundation of China(2242021);Strategic Priority Research Program (A) of the Chinese Academy of Sciences(XDA0390403);National Natural Science Foundation of China(U22A20416)

摘要/Abstract

摘要：

利用可再生电力将CO₂转化为高附加值化学品, 是协同实现碳减排与可持续化工合成的关键技术路径. 碳酸二甲酯(DMC)是重要的羰基化合物, 广泛应用于生物柴油、燃油添加剂、聚碳酸酯及锂离子电池电解液领域, 是串联CO₂资源化利用与储能技术的关键中间体. CO₂与甲醇热催化直接合成DMC存在热力学不利(ΔG > 0)、反应条件苛刻、平衡转化率受限的缺陷, 电催化路径可在温和条件下通过电子介导氧化还原反应克服该壁垒, 实现DMC可持续绿色制备. 现有氧化还原中性电催化体系已发展出金片、镍单原子、Co-CPY/CNT、B-Pd等阴极CO₂还原材料, 液相羰基化过程则主要依靠电解液中的钯基催化剂. 该耦合体系尚存两大关键难题: 一是阴极材料、羰基化催化剂与电解液需在CO₂还原、阳极氧化及羰基化反应耦合的复杂网络中协同运作, 界面不匹配现象和兼容性问题易在体系中传递放大; 二是动态运行条件下活性位点的精准调控难以实现, 限制了催化剂利用效率的提升.

针对耦合体系界面协同差、活性位点动态调控困难的问题, 本文以聚离子液体(PIL)为前驱体制备富吡咯氮碳阴极(NC-PIL)材料, 通过对电解液中微量Pd离子原位动态锚定, 构建具有自优化特性的CO₂电催化制DMC体系. 相较于尿素、三聚氰胺等常规氮源, PIL分子结构可精准调控, 改变阴离子种类能定向合成富吡咯氮的碳材料. 吡咯氮嵌入五元共轭碳环、氮原子孤对电子可与碳骨架共轭π轨道耦合, 兼具Pd离子捕获与电子调控双重作用, 这是吡啶氮、石墨氮不具备的独特优势, 也是实现体系自优化的结构基础. 自优化电解过程中, 阴极表面丰富的吡咯氮位点可在外加电位下持续捕获和再分散电解液中的Pd物种, 实时调节活性中心的分散状态与电子结构. 与传统催化剂活性位点“一经制备便固定化”、长期电解中易烧结团聚而失活不同, 本材料依靠吡咯氮动态优化重塑催化位点, 同步耦合CO₂还原与甲醇羰基化, 高选择性生成DMC. 基于该体系的自优化机制, 体系连续电解6 h仍可维持75%的DMC法拉第效率, 极低Pd用量下性能优于传统预制催化剂, 证实原位动态调控金属活性中心的设计策略具备显著优势.

综上, 本工作揭示了涵盖动态演化、反应耦合与界面重构的自优化行为, 验证了"动态导向"催化设计理念; 而PIL精准合成策略则突破了传统静态稳定性设计的局限, 为CO₂电催化的多组分耦合体系的高效设计开发提供了新思路.

关键词: 催化剂动态演化, 富吡咯氮碳材料, 聚离子液体导向合成, 二氧化碳电催化转化, 碳酸二甲酯

Abstract:

The electrocatalytic conversion of CO₂ and methanol to dimethyl carbonate (DMC) offers a sustainable route for CO₂ utilization, circumventing the thermodynamic constraints of thermal processes. However, current redox-neutral electrocatalytic systems face challenges in achieving catalyst-electrolyte compatibility and precise active-site control under dynamic electrochemical conditions. Here we report a self-optimizing electrocatalytic system for CO₂ to DMC conversion, enabled by a pyrrolic-N-rich carbon cathode derived from bromide-containing poly(ionic liquids) (PILs). Trace Pd ions deliberately introduced into the electrolyte are in-situ captured by pyrrolic nitrogen motifs, achieving the dynamic catalyst evolution with reaction progression. The pyrrolic nitrogen dynamically modulates the electronic structure of anchored Pd species, refining active-site dispersion and synergistically coupling CO₂ electroreduction with methanol carbonylation to yield DMC selectively. The system achieves a Faradaic efficiency of 75% for DMC over 6 h with minimal Pd usage, outperforming conventional pre-fabricated catalysts. This work unveils a "design-for-dynamics" paradigm wherein PIL-directed precision synthesis encodes dynamic responsiveness into the catalytic interface for sustainable CO₂ conversion.

Key words: Dynamic catalyst evolution, Pyrrolic-nitrogen-rich carbon, Poly(ionic liquid)-directed synthesis, Electrocatalytic CO₂ conversion, Dimethyl carbonate

李勇, 刘一凡, 乔翠, 付梦倩, 杨子锋, 李雨浓, 张锁江. 聚离子液体-富吡咯氮碳材料锚定痕量钯实现自优化CO₂制DMC电催化过程[J]. 催化学报, 2027, 92: 340-354.

Yong Li, Yifan Liu, Cui Qiao, Mengqian Fu, Zifeng Yang, Yunong Li, Suojiang Zhang. Poly(ionic liquid)-directed pyrrolic-N-rich carbon for trace-Pd anchoring toward self-optimizing CO₂-to-DMC electrocatalysis[J]. Chinese Journal of Catalysis, 2027, 92: 340-354.

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链接本文: https://www.cjcatal.com/CN/10.1016/S1872-2067(26)65267-9

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图/表 16

Fig. 1. Schematic illustration of the self-optimizing CO2-to-DMC electrocatalytic system enabled by in-situ Pd capture and pyrrolic-N sites.

Fig. 2. Synthetic procedure for the NC-PILs material.

Fig. 3. SEM images of NC-PVimBF4 (a‒c), NC-PVimPF6 (d‒f), NC-PVimCN (g‒i), and NC-PVimBr (j‒l).

Fig. 4. Characterization of XRD patterns (a), Raman spectra (b), high-resolution XPS spectra of the N 1s region (c) and content of pyridine N and pyrrole N (d) of NC-PILs.

Fig. 5. High-resolution Br 3d XPS spectra of NC-PVimBr (a), N 1s XPS spectra of NC-PVimBr and NC-PVimCN calcined under temperatures of 400 °C (b), 600 °C (c), and 900 °C (d) and percentage content of pyridine N and pyrrole Nat 400, 600, and 900 °C (e).

Fig. 6. Schematic of the NC-PVimBr formation derived by PIL.

Fig. 7. Characterizations of Pd/AC by TEM images (a), HR-TEM images (b,c), high-resolution Pd 3d XPS spectra (d) and N2 adsorption-desorption isotherms with pore size distribution (e).

Fig. 8. Electrochemical performance of NC-PIL. (a) DMC FE for different substrate materials. (b) DMC FE of NC‑PVimBr at potentials ranging from -1.8 to -2.1 V vs. Ag/AgCl. (c) DMC FE under different Pd/AC catalyst loadings. (d) DMC FE over multiple consecutive cycles. (e) Long‑term stability test of DMC FE. (f) Stability test performed at a constant current density of 12 mA cm‒2 in single cell.

Fig. 9. Control experiments with and without Pd/AC in both single-cell and H-cell configurations (Electrolyte: 0.1 mol L‒1 NaBr in CH3OH).

Fig. 10. TEM and HRTEM images of the cathode after reaction (a‒c) and TEM-EDS images of the cathode after reaction (d‒g).

Fig. 11. High-resolution XPS spectra of the Pd 3d region (a), Pd deposition amount over time (b), Pd content in electrolyte solution and on cathode with different Pd-based catalysts (c), the temporal evolution of FE for H2 and CO (d), FECO versus Pd deposition amount (e), andLSV of NC-PVimBr and Pd-NC-PVimBr in CO2-saturated 0.1 mol L‒1 NaBr-CH3OH in H-type cells for electrocatalytic CO2RRs (f).

Fig. 12. CO2RR pathways and theoretical calculations: pathway on Pd-C (a), pathway on C-pyridinic N-Pd (Pd-Py) (b), pathway on C-pyrrolic N-Pd (Pd-Pr) (c), adsorption energies of Pd on C, pyridinic N, and pyrrolic N (d), and Gibbs free energies over Pd-C, Pd-Py, and Pd-Pr (e).

Fig. 13. Charge density difference plots and Bader charge analysis for the three catalyst models. (a-c) Side view and top view of the bare Pd-support systems for Pd-C, Pd-Py, and Pd-Pr, with the corresponding electron transfer from the Pd cluster. (d-f) Side view and top view of the CO2-adsorbed systems (Pd-C-CO2*, Pd-Py-CO2*, and Pd-Pr-CO2*), with the corresponding charge transfer to CO2. Yellow and cyan isosurfaces represent electron accumulation and depletion, respectively.

Fig. 14. Proposed reaction pathways for CH3OH dissociation and related energies on Pd-C (a), on Pd-Py (b), on Pd-Pr (c). Adsorption energy of CO2 and dissociation energy of CH3OH (d) for H* formation on Pd-C, Pd-Py, and Pd-Pr.

Fig. 15. In-situ ATR-FTIR spectra collected on the NC-PVimBr electrode with in situ electrodeposited Pd species in CO2-saturated 0.1 mol L‒1 NaBr methanol electrolyte at applied potentials from -1.5 to -2.2 V vs. Ag/AgCl.

Fig. 16. Possible reaction mechanism of the electrocatalytic synthesis of DMC.

参考文献

[1]	R. G. Grim, Z. Huang, M. T. Guarnieri, J. R. Ferrell, L. Tao, J. A. Schaidle, Energy Environ. Sci., 2020, 13, 472-494.
[2]	A. Xu, S.-F. Hung, A. Cao, Z. Wang, N. Karmodak, J. E. Huang, Y. Yan, A. Sedighian Rasouli, A. Ozden, F.-Y. Wu, Z.-Y. Lin, H.-J. Tsai, T.-J. Lee, F. Li, M. Luo, Y. Wang, X. Wang, J. Abed, Z. Wang, D.-H. Nam, Y. C. Li, A. H. Ip, D. Sinton, C. Dong, E. H. Sargent, Nat. Catal., 2022, 5, 1081-1088.
[3]	J. H. Jang, C. Kim, O. S. Nayal, J. Bin Yeo, G. R. Kim, J. Kim, Y. I. Jo, U. Lee, M. S. Kwon, K. T. Nam, Nat. Synth., 2024, 3, 846-857.
[4]	X.-F. Liu, K. Zhang, L. Tao, X.-B. Lu, W.-Z. Zhang, Green Chem. Eng., 2022, 3, 125-137.
[5]	X.-Q. Li, G.-Y. Duan, J.-W. Chen, L.-J. Han, S.-J. Zhang, B.-H. Xu, Appl. Catal. B, 2021, 297, 120471.
[6]	Z. Mei, K. Chen, Y. Tan, Q. Liu, Q. Chen, Q. Wang, X. Wang, C. Cai, K. Liu, J. Fu, M. Liu, Chin. J. Catal., 2024, 62, 190-197.
[7]	P. Tundo, M. Musolino, F. Aricò, Green Chem., 2018, 20, 28-85.
[8]	F.-L. Zeng, H.-L. Zhu, X.-L. Chen, L.-B. Qu, B. Yu, Green Chem., 2021, 23, 3677-3682.
[9]	K. Xuan, Y. Pu, F. Li, J. Luo, N. Zhao, F. Xiao, Chin. J. Catal., 2019, 40, 553-566.
[10]	B. J. V. Davies, M. Šarić, M. C. Figueiredo, N. C. Schjødt, S. Dahl, P. G. Moses, M. Escudero-Escribano, M. Arenz, J. Rossmeisl, ACS Catal., 2019, 9, 859-866.
[11]	L. Dong, S. Zhu, Y. Yuan, X. Zhang, X. Zhao, Y. Chen, L. Xu, Chin. J. Catal., 2024, 65, 138-152.
[12]	L. Tian, Y.-S. Liao, Z. Xiao, G. Sun, J.-P. Chou, C.-Y. Wong, J. C. Ho, Y. Zhao, P.-T. Chou, Y.-K. Peng, ACS Catal., 2024, 14, 16861-16871.
[13]	D. Anastasiadou, E. J. M. Hensen, M. C. Figueiredo, Chem. Commun., 2020, 56, 13082-13092.
[14]	K. M. Lee, J. H. Jang, M. Balamurugan, J. E. Kim, Y. I. Jo, K. T. Nam, Nat. Energy, 2021, 6, 733-741.
[15]	X. Li, S.-G. Han, W. Wu, K. Zhang, B. Chen, S.-H. Zhou, D.-D. Ma, W. Wei, X.-T. Wu, R. Zou, Q.-L. Zhu, Energy Environ. Sci., 2023, 16, 502-512.
[16]	S.-G. Han, S. Zhou, X. Li, J. Zhao, W.-B. Wei, L. Zheng, D.-D. Ma, X.-T. Wu, Q.-L. Zhu, Chem. Eng. J., 2024, 486, 150179.
[17]	K.-A. Wang, Z.-L. Wang, H.-C. Hu, H.-B. Zhu, H. Yang, Chem. Eng. J., 2024, 498, 155109.
[18]	H.-Z. Tan, Z.-N. Chen, Z.-N. Xu, J. Sun, Z.-Q. Wang, R. Si, W. Zhuang, G.-C. Guo, ACS Catal., 2019, 9, 3595-3603.
[19]	R. Jin, G. Li, S. Sharma, Y. Li, X. Du, Chem. Rev., 2021, 121, 567-648.
[20]	Z. W. Seh, J. Kibsgaard, C. F. Dickens, I. Chorkendorff, J. K. Nørskov, T. F. Jaramillo, Science, 2017, 355, eaad4998.
[21]	B. Qiao, A. Wang, X. Yang, L. F. Allard, Z. Jiang, Y. Cui, J. Liu, J. Li, T. Zhang, Nat. Chem., 2011, 3, 634-641.
[22]	C. Xie, Z. Niu, D. Kim, M. Li, P. Yang, Chem. Rev., 2020, 120, 1184-1249.
[23]	C. Lin, Y. Liu, X. Kong, Z. Geng, J. Zeng, Nano Res., 2022, 15, 10078-10083.
[24]	W. Ju, A. Bagger, G.-P. Hao, A. S. Varela, I. Sinev, V. Bon, B. Roldan Cuenya, S. Kaskel, J. Rossmeisl, P. Strasser, Nat. Commun., 2017, 8, 944.
[25]	C. He, Y. Zhang, Y. Zhang, L. Zhao, L.-P. Yuan, J. Zhang, J. Ma, J.-S. Hu, Angew. Chem. Int. Ed., 2020, 59, 4914-4919.
[26]	S. Martínez, L. Veth, B. Lainer, P. Dydio, ACS Catal., 2021, 11, 3891-3915.
[27]	T.-P. Fellinger, A. Thomas, J. Yuan, M. Antonietti, Adv. Mater., 2013, 25, 5838-5855.
[28]	R. Sun, K. M. Meek, H. C. Ho, Y. A. Elabd, Polym. Int., 2019, 68, 1599-1609.
[29]	M. Fu, W. Ding, Q. Zhao, Z. Xu, W. Hua, Y. Li, Z. Yang, L. Dong, Q. Su, W. Cheng, Sep. Purif. Technol., 2024, 344, 127174.
[30]	J. Gong, H. Lin, M. Antonietti, J. Yuan, J. Mater. Chem. A, 2016, 4, 7313-7321.
[31]	Y. Liang, Y. Zhou, J. Ma, J. Zhao, Y. Chen, Y. Tang, T. Lu, Appl. Catal. B, 2011, 103, 388-396.
[32]	G. J. Brug, A. L. G. van den Eeden, M. Sluyters-Rehbach, J. H. Sluyters, J. Electroanal. Chem. Interfacial Electrochem., 1984, 176, 275-295.
[33]	M. D. Stoller, R. S. Ruoff, Energy Environ. Sci., 2010, 3, 1294-1297.
[34]	C. C. L. McCrory, S. Jung, J. C. Peters, T. F. Jaramillo, J. Am. Chem. Soc., 2013, 135, 16977-16987.
[35]	K. Zou, Y. Deng, J. Chen, Y. Qian, Y. Yang, Y. Li, G. Chen, J. Power Sources, 2018, 378, 579-588.
[36]	K. Li, W. Chen, H. Yang, Y. Chen, S. Xia, M. Xia, X. Tu, H. Chen, Bioresour. Technol., 2019, 280, 260-268.
[37]	P. Lazar, R. Mach, M. Otyepka, J. Phys. Chem. C, 2019, 123, 10695-10702.
[38]	S. Fu, M. Li, W. de Jong, R. Kortlever, ACS Catal., 2023, 13, 10309-10323.
[39]	H. Jiang, L. Liu, K. Zhao, Z. Liu, X. Zhang, S. Hu, Electrochim. Acta, 2020, 337, 135758.
[40]	M. Wang, Y. Zeng, G. Dong, C. Wang, Chin. J. Catal., 2020, 41, 1498-1510.
[41]	A. Sato, K. Gotoh, S. Sato, Y. Yamada, Carbon, 2024, 222, 118904.
[42]	J. Chen, J. Zhong, Y. Wu, W. Hu, P. Qu, X. Xiao, G. Zhang, X. Liu, Y. Jiao, L. Zhong, Y. Chen, ACS Catal., 2020, 10, 10339-10349.
[43]	X. Chen, G. Wu, J. Chen, X. Chen, Z. Xie, X. Wang, J. Am. Chem. Soc., 2011, 133, 3693-3695.
[44]	K. Q. Vuong, R. Effenberger, J. Zilberman, S. Smart, C. M. Williams, E. W. McFarland, ACS Sustainable Chem. Eng., 2017, 5, 7492-7495.
[45]	J.-C. Choi, L.-N. He, H. Yasuda, T. Sakakura, Green Chem., 2002, 4, 230-234.
[46]	Liu , F. Takemura, A. Yabe, J. Chem. Eng. Data, 1996, 41, 589-592.
[47]	F. Wu, Q. Zhao, L. Tao, D. Danaci, P. Xiao, F. A. Hasan, P. A. Webley, J. Chem. Eng. Data, 2019, 64, 5609-5621.

聚离子液体-富吡咯氮碳材料锚定痕量钯实现自优化CO₂制DMC电催化过程

Poly(ionic liquid)-directed pyrrolic-N-rich carbon for trace-Pd anchoring toward self-optimizing CO₂-to-DMC electrocatalysis

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[12]	杜治平, 周彬, 黄丽明, 黄晨, 吴元欣, 王存文, 孙炜. Cu(phen)Cl₂ 催化甲醇氧化羰基化合成碳酸二甲酯[J]. 催化学报, 2012, 33(4): 736-742.
[13]	潘赛勇, 郑丽萍, 聂仁峰, 夏水鑫, 陈平, 侯昭胤. 碱性分子筛作用下甘油与碳酸二甲酯反应制碳酸甘油酯[J]. 催化学报, 2012, 33(11): 1772-1777.
[14]	王瑞玉;李忠;郑华艳;谢克昌. 无氯 Cu/AC 催化剂的制备及其催化气相甲醇氧化羰基化反应性能[J]. 催化学报, 2010, 31(7): 851-856.
[15]	李忠;刘树森;任军;牛燕燕;郑华艳;赵强;崔丽萍. CuCl/SiO2-TiO2 催化剂的结构及其催化甲醇氧化羰基化反应性能[J]. 催化学报, 2010, 31(6): 683-688.