Ag-Sn间电子结构调控在酸性环境中实现1 A/cm2下高效CO2还原

doi:10.11949/0438-1157.20250288

摘要/Abstract

摘要：

酸性条件下的电催化二氧化碳还原（CO₂RR）因其能够提高CO₂利用率并抑制碳酸盐形成而备受关注。然而，酸性环境由于H⁺浓度升高导致竞争性析氢反应（HER）加剧，从而对催化剂的稳定性和选择性提出了更高的要求。在此，报道了一种Ag-Sn双金属催化剂，在pH=2的酸性膜电极中表现出了优异的CO₂RR性能。该催化剂在400 mA/cm²的电流密度下CO选择性高达99.4%，且在1 A/cm²的条件下，CO的法拉第效率（FE_CO）仍能维持在83.5%，CO的分电流密度最高达到了834.8 mA/cm²。研究发现，少量Sn的引入能够调节Ag的电子结构，从而加速CO₂活化以及向*COOH中间体的转变。这项工作为开发适用于酸性条件的高效稳定CO₂RR催化剂提供了新的思路。

关键词: 酸性, 电催化CO₂还原, MEA, 法拉第效率, CO分电流密度, 电子结构, 活化, 中间体

Abstract:

Electrocatalytic CO₂ reduction under acidic conditions has attracted significant attention due to its ability to enhance CO₂ utilization and suppress carbonate formation. However, the elevated H⁺ concentration in acidic environments intensifies the competing hydrogen evolution reaction (HER), thereby imposing higher requirements on catalyst stability and selectivity. Herein, we report an Ag-Sn bimetallic catalyst that exhibits outstanding CO₂RR performance in an acidic membrane electrode assembly (MEA) at pH=2. Under a current density of 400 mA/cm², the catalyst achieves a CO selectivity of up to 99.4%, and even at 1 A/cm², the CO Faraday efficiency (FE_CO) remains at 83.5%, with a maximum CO partial current density reaching 834.8 mA/cm². The study found that the introduction of a small amount of Sn can adjust the electronic structure of Ag, thereby accelerating the activation of CO₂ and the transformation to *COOH intermediates. This work provides a new strategy for developing highly efficient and stable CO₂RR catalysts suitable for operation under acidic conditions.

Key words: acid, electrocatalytic carbon dioxide reduction, MEA, Faraday efficiency, CO partial current density, electronic structure, activation, intermediate

中图分类号:

TQ 151.1

彭郅众, 郎学磊, 房强, 井慧芳, 钟达忠, 李晋平, 赵强. Ag-Sn间电子结构调控在酸性环境中实现1 A/cm²下高效CO₂还原[J]. 化工学报, 2025, 76(12): 6376-6386.

Zhizhong PENG, Xuelei LANG, Qiang FANG, Huifang JING, dazhong ZHONG, Jinping LI, Qiang ZHAO. Ag-Sn interfacial electronic structure modulation for high-efficiency CO₂ electroreduction at 1 A/cm² under acidic conditions[J]. CIESC Journal, 2025, 76(12): 6376-6386.

图/表 15

图1 MEA电解槽示意图

Fig.1 Schematic of MEA cell

图2 Ag-Sn1.4%的制备流程图

Fig.2 The scheme for the preparation of Ag-Sn1.4%

图3 (a) Ag-Sn及Ag NP的XRD谱图；(b~d) Ag-Sn4.9%，Ag-Sn1.4%，Ag-Sn0.2%的XPS谱图

Fig.3 (a) XRD of Ag-Sn and Ag NP; XPS for (b) Ag-Sn4.9%; (c) Ag-Sn1.4%; (d) Ag-Sn0.2%

图4 (a)Ag NP、(b)Ag-Sn0.2%、(c)Ag-Sn1.4%、(d)Ag-Sn4.9%的扫描电镜图

Fig.4 SEM of (a) Ag NP, (b) Ag-Sn0.2%, (c) Ag-Sn1.4%, (d) Ag-Sn4.9%

图5 (a)Ag-Sn1.4%的透射电镜图；(b)Ag-Sn1.4%的高分辨率透射电镜图；(c)Ag NP的透射电镜图；(d)Ag NP的高分辨率透射电镜图

Fig.5 (a) TEM of Ag-Sn1.4%; (b) HRTEM of Ag-Sn1.4%; (c) TEM of Ag NP; (d) HRTEM of Ag NP

图6 Ag-Sn1.4%的mapping图

Fig.6 Mapping of Ag-Sn1.4%

图7 双电层电容测试

Fig.7 ECSA

图8 Ag NP和Ag-Sn1.4%在不同扫速下的Cdl值

Fig.8 Cdl of Ag-Sn1.4% and Ag NP

图9 (a)合成过程中反应液的pH及Ag-Sn催化剂的负载量对催化性能的影响；(b)Ag-Sn催化剂在50 mA/cm2下进行的预还原过程

Fig.9 (a) Effect of pH of reaction solution during synthesis and loading of Ag-Sn catalyst on catalytic performance; (b) Pre-reduction process of Ag-Sn at 50 mA/cm2

图10 法拉第效率及电压

Fig.10 FE and potential

图11 (a)在400 mA/cm2和1 A/cm2下不同Sn含量样品的对比图；(b)CO分电流密度

Fig.11 (a) Comparison of samples with different Sn contents at 400 mA/cm2 and 1 A/cm2; (b) CO partial current density

表1 膜电极CO2RR活性对比

Table 1 Comparison of catalytic activity in MEA

Catalyst	J_Total/(mA/cm²)	Electrolyte	FE_CO/%	Ref.
Ag-Sn_1.4%	1000	K₂SO₄+ H₂SO₄	83.5	this work
Ag-Sn_1.4%	400	K₂SO₄+ H₂SO₄	99.4	this work
Ni-N-C	500	K₂SO₄+ H₂SO₄	约80	[30]
Ag	60	Cs₂SO₄+ H₂SO₄	约80	[31]
Ag@C-d	200	K₂SO₄+ H₂SO₄	91.6	[32]
Ag∶Cs-DC	400	KHCO₃	81.6	[33]
Ni₁-NSC	225	KOH	约100	[34]

图12 (a)Ag-Sn1.4%与Ag NP的能量效率；(b)Ag-Sn1.4%的单程碳效率；(c)Ag-Sn1.4%在pH=2下的稳定性测试

Fig.12 (a) Energy efficiency of Ag-Sn1.4% and Ag NP; (b) SPCE of Ag-Sn1.4%; (c) Stability test of Ag-Sn1.4% at pH=2

图13 Ag-Sn1.4%（a）和Ag NP（b）的原位拉曼光谱图

Fig.13 In situ Raman spectroscopy of Ag-Sn1.4%(a) and Ag NP(b)

图14 Ag-Sn1.4%（a）和Ag NP的Ag 3d XPS光谱图

Fig.14 Ag 3d XPS spectra of Ag-Sn1.4% and Ag NP

参考文献 41

[1]	Leveni M, Bielicki J M. A potential for climate benign direct air CO₂ capture with CO₂-driven geothermal utilization and storage (DACCUS)[J]. Environmental Research Letters, 2023, 19(1): 014007.
[2]	Li C, Zhang T F, Qiu Z, et al. Plasma-assisted fabrication of multiscale materials for electrochemical energy conversion and storage[J]. Carbon Energy, 2025, 7(2): e641.
[3]	Yun H, Yoo S, Son J, et al. Strong cation concentration effect of Ni-N-C electrocatalysts in accelerating acidic CO₂ reduction reaction[J]. Chem, 2025. DOI: 10.10161j.Chempr.2025.102461
[4]	Terholsen D H, Huerta-Zerón H D, Möller C, et al. Photocatalytic CO₂ reduction using CO₂-binding enzymes[J]. Angewandte Chemie International Edition, 2024, 63(16): e202319313.
[5]	Bai S T, De Smet G, Liao Y H, et al. Homogeneous and heterogeneous catalysts for hydrogenation of CO₂ to methanol under mild conditions[J]. Chemical Society Reviews, 2021, 50(7): 4259-4298.
[6]	Diehl T, Lanzerath P, Franciò D G, et al. A self-separating multiphasic system for catalytic hydrogenation of CO₂ and CO₂-derivatives to methanol[J]. ChemSusChem, 2022, 15(22): e202201250.
[7]	Pang Q Q, Fan X Z, Sun K H, et al. Nickel-nitrogen-carbon (Ni-N-C) electrocatalysts toward CO₂ electroreduction to CO: advances, optimizations, challenges, and prospects[J]. Energy & Environmental Materials, 2024, 7(5): e12731.
[8]	Weng C C, Wang C, Song Y, et al. In-situ reconstruction of active bismuth for enhanced CO₂ electroreduction to formate[J]. Chemical Engineering Journal, 2025, 505: 159732.
[9]	Zhang N, Zhang Y L. Recent advances in electrocatalytic conversion of CO₂-to-ethylene: from reaction mechanisms to tuning strategies[J]. Applied Catalysis B: Environment and Energy, 2025, 363: 124822.
[10]	Zhou J, He B L, Huang P, et al. Regulating interfacial hydrogen-bonding networks by implanting Cu sites with perfluorooctane to accelerate CO₂ electroreduction to ethanol[J]. Angewandte Chemie International Edition, 2024, 137(6): e202418459.
[11]	Gong S H, Han X, Li W S, et al. Paired electrolysis for efficient coproduction of CO and S8 with techno-economic analysis[J]. Chemical Engineering Journal, 2025, 507: 160286.
[12]	Huang J E, Li F W, Ozden A, et al. CO₂ electrolysis to multicarbon products in strong acid[J]. Science, 2021, 372(6546): 1074-1078.
[13]	Gu J, Liu S, Ni W Y, et al. Modulating electric field distribution by alkali cations for CO₂ electroreduction in strongly acidic medium[J]. Nature Catalysis, 2022, 5: 268-276.
[14]	Su L N, Hua Q F, Yang Y N, et al. Regulating competing reaction pathways for efficient CO₂ electroreduction in acidic conditions[J]. Journal of Energy Chemistry, 2025, 105: 326-351.
[15]	Hernandez-Aldave S, Andreoli E. Fundamentals of gas diffusion electrodes and electrolysers for carbon dioxide utilisation: challenges and opportunities[J]. Catalysts, 2020, 10(6): 713.
[16]	Jouny M, Luc W, Jiao F,et al. General techno-economic analysis of CO₂ electrolysis systems[J]. Industrial & Engineering Chemistry Research, 2018, 57(6): 2165-2177.
[17]	Gabardo C M, O'Brien C P, Edwards J P, et al. Continuous carbon dioxide electroreduction to concentrated multi-carbon products using a membrane electrode assembly[J]. Joule, 2019, 3(11): 2777-2791.
[18]	De Luna P, Hahn C, Higgins D, et al. What would it take for renewably powered electrosynthesis to displace petrochemical processes?[J]. Science, 2019, 364(6438): eaav3506.
[19]	Jiang Y L, Huang L S, Chen C J, et al. Catalyst-electrolyte interface engineering propels progress in acidic CO₂ electroreduction[J]. Energy & Environmental Science, 2025, 18(5): 2025-2049.
[20]	Goyal A, Marcandalli G, Mints V A, et al. Competition between CO₂ reduction and hydrogen evolution on a gold electrode under well-defined mass transport conditions[J]. Journal of the American Chemical Society, 2020, 142(9): 4154-4161.
[21]	Liu Z K, Yan T, Shi H, et al. Acidic electrocatalytic CO₂ reduction using space-confined nanoreactors[J]. ACS Applied Materials & Interfaces, 2022, 14(6): 7900-7908.
[22]	Sheng X D, Ge W X, Jiang H L, et al. Engineering the Ni-N-C catalyst microenvironment enabling CO₂ electroreduction with nearly 100% CO selectivity in acid[J]. Advanced Materials, 2022, 34(38): 2201295.
[23]	Singh M R, Goodpaster J D, Weber A Z, et al. Mechanistic insights into electrochemical reduction of CO₂ over Ag using density functional theory and transport models[J]. Proceedings of the National Academy of Sciences of the United States of America, 2017, 114(42): E8812-E8821.
[24]	Wu X H, Guo Y N, Sun Z S, et al. Fast operando spectroscopy tracking in situ generation of rich defects in silver nanocrystals for highly selective electrochemical CO₂ reduction[J]. Nature Communications, 2021, 12(1): 660.
[25]	Ren D W, Xu D A, Chan P K, et al. A cation concentration gradient approach to tune the selectivity and activity of CO₂ electroreduction[J]. Angewandte Chemie International Edition, 2022, 134(49): e202214173.
[26]	Cai C, Liu B, Liu K, et al. Heteroatoms induce localization of the electric field and promote a wide potential-window selectivity towards CO in the CO₂ electroreduction[J]. Angewandte Chemie International Edition, 2022, 61(44): e202212640.
[27]	Dai R Y, Sun K A, Shen R A, et al. Direct microenvironment modulation of CO₂ electroreduction: negatively charged Ag sites going beyond catalytic surface reactions[J]. Angewandte Chemie International Edition, 2024, 63(37): e202408580.
[28]	Bokuniaeva A O, Vorokh A S. Estimation of particle size using the Debye equation and the Scherrer formula for polyphasic TiO₂ powder[J]. Journal of Physics: Conference Series, 2019, 1410(1): 012057.
[29]	Sandoval M G, Walia J, Houache M S E, et al. CO₂ adsorption and activation on Ag(111) surfaces in the presence of surface charge density: a static gas phase DFT study[J]. Applied Surface Science, 2023, 610: 155498.
[30]	Li H F, Li H B, Wei P F, et al. Tailoring acidic microenvironments for carbon-efficient CO₂ electrolysis over a Ni-N-C catalyst in a membrane electrode assembly electrolyzer[J]. Energy & Environmental Science, 2023, 16(4): 1502-1510.
[31]	Pan B B, Fan J, Zhang J, et al. Close to 90% single-pass conversion efficiency for CO₂ electroreduction in an acid-fed membrane electrode assembly[J]. ACS Energy Letters, 2022, 7(12): 4224-4231.
[32]	Zhang B, Zou J H, Chen Z H, et al. Defect-engineered carbon-confined silver for enhanced CO₂ electrocatalytic reduction to CO in acidic media[J]. Next Nanotechnology, 2023, 2: 100014.
[33]	Sun Y H, Chen P J, Du X M, et al. Anchoring Cs⁺ ions on carbon vacancies for selective CO₂ electroreduction to CO at high current densities in membrane electrode assembly electrolyzers[J]. Angewandte Chemie International Edition, 2024, 63(40): e202410802.
[34]	Chen Z Y, Wang C H, Zhong X, et al. Achieving efficient CO₂ electrolysis to CO by local coordination manipulation of nickel single-atom catalysts[J]. Nano Letters, 2023, 23(15): 7046-7053.
[35]	Han J Y, Bai X, Xu X Q, et al. Advances and challenges in the electrochemical reduction of carbon dioxide[J]. Chemical Science, 2024, 15(21): 7870-7907.
[36]	Bohra D, Ledezma-Yanez I, Li G N, et al. Lateral adsorbate interactions inhibit HCOO^- while promoting CO selectivity for CO₂ electrocatalysis on silver[J]. Angewandte Chemie International Edition, 2019, 58(5): 1345-1349.
[37]	Chernyshova I V, Somasundaran P, Ponnurangam S. On the origin of the elusive first intermediate of CO₂ electroreduction[J]. Proceedings of the National Academy of Sciences of the United States of America, 2018, 115(40): E9261-E9270.
[38]	Lin Y X, Wang S C, Liu H J, et al. Regulating the electrocatalytic active centers for accelerated proton transfer towards efficient CO₂ reduction[J]. National Science Review, 2025, 12(3): nwaf010.
[39]	Feng S J, Wang X J, Cheng D F, et al. Stabilizing *CO₂ intermediates at the acidic interface using molecularly dispersed cobalt phthalocyanine as catalysts for CO₂ reduction[J]. Angewandte Chemie International Edition, 2024, 63(8): e202317942.
[40]	Liu H M, Yan T, Tan S D, et al. Observation on microenvironment changes of dynamic catalysts in acidic CO₂ reduction[J]. Journal of the American Chemical Society, 2024, 146(8): 5333-5342.
[41]	Zamora Zeledón J A, Stevens M B, Gunasooriya G T K K, et al. Tuning the electronic structure of Ag-Pd alloys to enhance performance for alkaline oxygen reduction[J]. Nature Communications, 2021, 12(1): 620.

Ag-Sn间电子结构调控在酸性环境中实现1 A/cm²下高效CO₂还原

Ag-Sn interfacial electronic structure modulation for high-efficiency CO₂ electroreduction at 1 A/cm² under acidic conditions

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