Citation: Mulin Yu, Shuo Liu, Yufeng Tang, Guoqiang Lu, Linbo Liu, Pengfei Sui, Xianzhu Fu, Subiao Liu, Yifei Sun, Jingli Luo. Mediating electron delocalization of surface palladium atoms by diethylamine ligand for efficient CO₂ electroreduction[J]. Chinese Chemical Letters, ;2026, 37(3): 111958. doi: 10.1016/j.cclet.2025.111958 shu

Mediating electron delocalization of surface palladium atoms by diethylamine ligand for efficient CO₂ electroreduction

Mulin Yu ^a ,
Shuo Liu ^a ,
Yufeng Tang ^a ,
Guoqiang Lu ^a ,
Linbo Liu ^a ,
Pengfei Sui ^b ,
Xianzhu Fu ^c ,
Subiao Liu ^{a, *,} ,
Yifei Sun ^d ,
Jingli Luo ^{b, c}

a.
School of Minerals Processing and Bioengineering, Central South University, Changsha 410083, China
b.
Department of Chemical and Materials Engineering, University of Alberta, Edmonton, Alberta T6G 1H9, Canada
c.
College of Materials Science and Engineering, Shenzhen University, Shenzhen 518060, China
d.
College of Energy, Xiamen University, Xiamen 361005, China

subiao@csu.edu.cn

Received Date: 11 June 2025
Revised Date: 11 October 2025
Accepted Date: 13 October 2025
Available Online: 14 October 2025

Figures(5)

Functionalizing ligands on surface metal atoms has been implemented to tune the adsorption behaviors of intermediates in electrochemical CO₂ reduction reaction (CO₂RR). However, it is always bound within an unfavorable linear scaling relationship of the synchronously changed adsorption energies of intermediates. To break it, a win-win diethylamine (DEA)-mediated strategy was proposed to functionalize surface Pd atoms by exchanging the residual oleylamine (OAm) on ultrafine Pd nanoparticles (Pd NPs) with DEA. The molecular dynamics simulations, coupled with in situ Fourier transform infrared spectroscopy results, revealed that DEA hindered less toward CO₂ than H₂O on Pd NPs surface, and induced more CO linear configuration intermediate (*CO_L), indicative of ease CO₂ transport and CO desorption. Additionally, computational calculations implied that -NH- in DEA delocalized more electrons to surface Pd atoms and formed H-bond with *COOH, asynchronously changing the adsorption energies of *COOH and *CO, which enabled a CO Faraday efficiency (FE_CO) close to 100% in an ultrawide potential window and a stability of over 50 h with a FE_CO over 90%. This study dexterously addresses the residual issue of end-blocking agents on metal nanostructures from synthesis, and synchronously realizes the surface molecular functionalization, paving a smart avenue to design high-performance electrocatalysts.
- Electrochemical CO₂ reduction reaction,
- Ligand effect,
- Hydrogen bond,
- Pd electrocatalyst,
- Electron delocalization
1. [1]
  R. Li, C.W. Tung, B. Zhu, et al., J. Colloid Interface Sci. 674 (2024) 326–335. doi: 10.1016/j.jcis.2024.06.176
2. [2]
  R. Li, F. Xie, P. Kuang, et al., Small 20 (2024) 2402867. doi: 10.1002/smll.202402867
3. [3]
  Q. Cheng, M. Huang, Q. Ye, B. Deng, F. Dong, Chin. Chem. Lett. 35 (2024) 109112. doi: 10.1016/j.cclet.2023.109112
4. [4]
  D. Gao, H. Zhou, F. Cai, et al., ACS Catal. 8 (2018) 1510–1519. doi: 10.1021/acscatal.7b03612
5. [5]
  B. Jiang, X.G. Zhang, K. Jiang, D.Y. Wu, W.B. Cai, J. Am. Chem. Soc. 140 (2018) 2880–2889. doi: 10.1021/jacs.7b12506
6. [6]
  S. Chatterjee, C. Griego, J.L. Hart, et al., ACS Catal. 9 (2019) 5290–5301. doi: 10.1021/acscatal.9b00330
7. [7]
  J.S. Diercks, J. Herranz, M. Georgi, et al., ACS Catal. 12 (2022) 10727–10741. doi: 10.1021/acscatal.2c02660
8. [8]
  J. Fan, H. Du, Y. Zhao, et al., ACS Catal. 10 (2020) 13560–13583. doi: 10.1021/acscatal.0c03280
9. [9]
  J.T. Ren, L. Chen, H.Y. Wang, Y. Feng, Z.Y. Yuan, Energy Environ. Sci. 17 (2024) 3960–4009. doi: 10.1039/d3ee04251k
10. [10]
  X. Tan, C. Yu, X. Song, et al., Nano Energy 104 (2022) 107957. doi: 10.1016/j.nanoen.2022.107957
11. [11]
  D. Xiao, X. Bao, M. Zhang, et al., Chem. Eng. J. 452 (2023) 139358. doi: 10.1016/j.cej.2022.139358
12. [12]
  S. Liu, H. Tao, L. Zeng, et al., J. Am. Chem. Soc. 139 (2017) 2160–2163. doi: 10.1021/jacs.6b12103
13. [13]
  H. Zhang, C. He, S. Han, et al., Chin. Chem. Lett. 33 (2022) 3641–3649. doi: 10.1016/j.cclet.2021.12.018
14. [14]
  H. Jia, Y. Yang, T.H. Chow, et al., Adv. Funct. Mater. 31 (2021) 2101255. doi: 10.1002/adfm.202101255
15. [15]
  Y. Zhou, R. Zhou, X. Zhu, et al., Adv. Mater. 32 (2020) 2000992. doi: 10.1002/adma.202000992
16. [16]
  D. Wu, G. Huo, W. Chen, X.Z. Fu, J.L. Luo, Appl. Catal. B: Environ. 271 (2020) 118957. doi: 10.1016/j.apcatb.2020.118957
17. [17]
  W. Xie, B. Li, L. Liu, et al., Chem. Soc. Rev. 54 (2025) 898–959. doi: 10.1039/d4cs00563e
18. [18]
  F. Ye, S. Zhang, Q. Cheng, et al., Nat. Commun. 14 (2023) 2040. doi: 10.1038/s41467-023-37679-3
19. [19]
  M. Jiang, M. Zhu, M. Wang, et al., ACS Nano 17 (2023) 3209–3224. doi: 10.1021/acsnano.2c11046
20. [20]
  Y. Liu, Z. Jiang, C. Huang, et al., Nano Lett. 23 (2023) 5911–5918. doi: 10.1021/acs.nanolett.3c00703
21. [21]
  X. Kong, J. Zhao, Z. Xu, et al., J. Am. Chem. Soc. 145 (2023) 14903–14911. doi: 10.1021/jacs.3c04143
22. [22]
  M.N. Khrizanforov, F.F. Naileva, K.A. Ivshin, et al., Dalton Trans. 53 (2024) 17351–17360. doi: 10.1039/d4dt01181c
23. [23]
  J. Chen, G. Wang, Y. Dong, et al., Angew. Chem. Int. Ed. 64 (2025) e202416367. doi: 10.1002/anie.202416367
24. [24]
  V.V. Khrizanforova, R.R. Fayzullin, S.V. Kartashov, et al., Chem. Eur. J. 30 (2024) e202400168. doi: 10.1002/chem.202400168
25. [25]
  G. Yang, J. Huang, W. Gu, et al., Proc. Natl. Acad. Sci. U. S. A. 122 (2025) e2419434122. doi: 10.1073/pnas.2419434122
26. [26]
  X. Chen, J. Chen, N.M. Alghoraibi, et al., Nat. Catal. 4 (2021) 20–27.
27. [27]
  A. Thevenon, A. Rosas-Hernández, J.C. Peters, T. Agapie, Angew. Chem. 131 (2019) 17108–17114. doi: 10.1002/ange.201907935
28. [28]
  J. Tamura, A. Ono, Y. Sugano, C. Huang, et al., Phys. Chem. Chem. Phys. 17 (2015) 26072–26078. doi: 10.1039/C5CP03028E
29. [29]
  Q. Fan, K. Liu, Z. Liu, et al., Part. Part. Syst. Char. 34 (2017) 1700075. doi: 10.1002/ppsc.201700075
30. [30]
  Z. Wang, Y. Zhou, C. Xia, et al., Angew. Chem. 133 (2021) 19255–19260. doi: 10.1002/ange.202107523
31. [31]
  X.K. Qi, M.J. Zheng, C. Yang, et al., J. Am. Chem. Soc. 145 (2023) 16630–16641. doi: 10.1021/jacs.3c04073
32. [32]
  Z. Liu, X. Lv, S. Kong, et al., Angew. Chem. Int. Ed. 62 (2023) e202309319. doi: 10.1002/anie.202309319
33. [33]
  W. Chen, Y. Wang, F. Wang, et al., Adv. Mater. 36 (2024) 2411802. doi: 10.1002/adma.202411802
34. [34]
  S. Choi, S. Parameswaran, J. -H. Choi, Phys. Chem. Chem. Phys. 23 (2021) 12976–12987. doi: 10.1039/d1cp00634g
35. [35]
  Q. Luo, H. Duan, M.C. McLaughlin, et al., Chem. Sci. 14 (2023) 9664–9677. doi: 10.1039/d3sc02658b
36. [36]
  S. Yoo, S. Yoo, G. Deng, et al., Adv. Mater. 36 (2024) 2313032. doi: 10.1002/adma.202313032
37. [37]
  M. Dack, Chem. Soc. Rev. 4 (1975) 211–229. doi: 10.1039/cs9750400211
38. [38]
  E. Breynaert, M. Houlleberghs, S. Radhakrishnan, et al., Chem. Soc. Rev. 49 (2020) 2557–2569. doi: 10.1039/c9cs00545e
39. [39]
  Y. Wang, Y. Liu, P. Cao, et al., ACS Appl. Mater. Interfaces 16 (2024) 20587–20596. doi: 10.1021/acs.iecr.4c02081
40. [40]
  M. Zhuansun, Y. Liu, R. Lu, et al., Angew. Chem. 135 (2023) e202309875. doi: 10.1002/ange.202309875
41. [41]
  K. Chen, M. Cao, Y. Lin, et al., Adv. Funct. Mater. 32 (2022) 2111322. doi: 10.1002/adfm.202111322
42. [42]
  R. Li, H. Li, X. Zhang, et al., Adv. Funct. Mater. 34 (2024) 2402797. doi: 10.1002/adfm.202402797
43. [43]
  Z. Ouyang, G. Sheng, Y. Zhong, et al., Angew. Chem. Int. Ed. 64 (2025) e202418790. doi: 10.1002/anie.202418790
44. [44]
  S. Chen, S. Li, R. You, et al., ACS Catal. 11 (2021) 5666–5677. doi: 10.1021/acscatal.1c00839
45. [45]
  J. Luo, Y. Zhou, S. Yang, et al., ACS Appl. Mater. Interfaces 15 (2023) 22025–22035. doi: 10.1021/acsami.3c00163
46. [46]
  D. Hemmeter, U. Paap, N. Taccardi, et al., ChemPhysChem 24 (2023) e202200391. doi: 10.1002/cphc.202200391
47. [47]
  X. Xiao, S. Lin, L. Zhang, et al., Nano Res. 15 (2022) 2928–2934. doi: 10.1007/s12274-021-3905-y
48. [48]
  J. Huang, M. Klahn, X. Tian, et al., Angew. Chem. 136 (2024) e202400174. doi: 10.1002/ange.202400174
49. [49]
  J. Sun, H. Yang, W. Gao, T. Cao, G. Zhao, Angew. Chem. 134 (2022) e202211373. doi: 10.1002/ange.202211373
50. [50]
  Q. Chen, X. Zhou, X. Zhang, et al., ACS Appl. Mater. Interfaces 14 (2022) 20988–20996. doi: 10.1021/acsami.2c02329
51. [51]
  C. Feng, X. Ouyang, Y. Deng, J. Wang, L. Tang, J. Hazard. Mater. 441 (2023) 129845. doi: 10.1016/j.jhazmat.2022.129845
52. [52]
  H. Guo, J. Raj, Z. Wang, et al., Small 20 (2024) 2311132. doi: 10.1002/smll.202311132
53. [53]
  J.F. Xie, J.J. Chen, Y.X. Huang, et al., Appl. Catal. B: Environ. 270 (2020) 118864. doi: 10.1016/j.apcatb.2020.118864
54. [54]
  S. Wei, Y. Xu, T. Song, et al., J. Am. Chem. Soc. 147 (2025) 4219–4229. doi: 10.1021/jacs.4c14253
55. [55]
  L. Zhang, X. Yang, Q. Yuan, et al., Nat. Commun. 14 (2023) 8311. doi: 10.1038/s41467-023-44078-1
56. [56]
  C. Liu, M. Wang, J. Ye, et al., Nano Lett. 23 (2023) 1474–1480. doi: 10.1021/acs.nanolett.2c04911
57. [57]
  Q. Liu, Q. Jiang, L. Li, W. Yang, J. Am. Chem. Soc. 146 (2024) 4242–4251. doi: 10.1021/jacs.3c14129
58. [58]
  Z. Jin, M. Yang, Y. Dong, et al., Nano-Micro Lett. 16 (2024) 4. doi: 10.1007/s40820-023-01214-2
59. [59]
  N. Zhang, X. Zhang, Y. Kang, et al., Angew. Chem. 133 (2021) 13500–13505. doi: 10.1002/ange.202101559
1. [1]
  Yi-Chang Yang , Rui-Xi Wang , Li-Ming Wu , Ling Chen . Regulating the coplanarity of π-conjugated units through hydrogen bonding in FAHC2O4 and FAH2C3N3S3 crystals. Chinese Journal of Structural Chemistry, 2025, 44(10): 100714-100714. doi: 10.1016/j.cjsc.2025.100714
2. [2]
  Yun Zhou , Geqian Fang , Haiyan Wang , Wenjun Yu , Chun Zhu , Jin-Xia Liang , Jian Lin . Non-covalent interactions between adsorbed •OH species and UiO-66-NH2 for methane hydroxylation. Chinese Journal of Structural Chemistry, 2025, 44(8): 100629-100629. doi: 10.1016/j.cjsc.2025.100629
3. [3]
  Luyao Lu , Chen Zhu , Fei Li , Pu Wang , Xi Kang , Yong Pei , Manzhou Zhu . Ligand effects on geometric structures and catalytic activities of atomically precise copper nanoclusters. Chinese Journal of Structural Chemistry, 2024, 43(10): 100411-100411. doi: 10.1016/j.cjsc.2024.100411
4. [4]
  He Yao , Wenhao Ji , Yi Feng , Chunbo Qian , Chengguang Yue , Yue Wang , Shouying Huang , Mei-Yan Wang , Xinbin Ma . Copper-catalyzed and biphosphine ligand controlled 3,4-boracarboxylation of 1,3-dienes with carbon dioxide. Chinese Chemical Letters, 2025, 36(4): 110076-. doi: 10.1016/j.cclet.2024.110076
5. [5]
  Xiaoqin Du , Peiyao Pan , Haoqi Li , Di Zhang , Wentao Huang , Xi Kang , Manzhou Zhu . Assessing the photoluminescence of metal nanoclusters: The individual versus the collective. Chinese Chemical Letters, 2026, 37(2): 111155-. doi: 10.1016/j.cclet.2025.111155
6. [6]
  Qiao Zhang , Xin Tan , Zihang Liu , Jingyu Ma , Dongqi Cao , Fenfang Li , Shengyi Dong . Optically healable and mechanically tough supramolecular glass from low-molecular-weight compounds. Chinese Chemical Letters, 2025, 36(8): 110660-. doi: 10.1016/j.cclet.2024.110660
7. [7]
  Linlin Gan , Xuan Peng , Wenchao Zhai , Cheng Zhang , Xinyu Duan , Ke Deng , Wei Li , Qingdao Zeng . Regulatory effects of coronene and pyridine on the self-assembly structure of tetracarboxylic acid derivative formed by dimeric building blocks. Chinese Chemical Letters, 2026, 37(3): 110667-. doi: 10.1016/j.cclet.2024.110667
8. [8]
  Min Song , Qian Zhang , Tao Shen , Guanyu Luo , Deli Wang . Surface reconstruction enabled o-PdTe@Pd core-shell electrocatalyst for efficient oxygen reduction reaction. Chinese Chemical Letters, 2024, 35(8): 109083-. doi: 10.1016/j.cclet.2023.109083
9. [9]
  Xuyun Lu , Yanan Chang , Shasha Wang , Xiaoxuan Li , Jianchun Bao , Ying Liu . Hydrogen peroxide electrosynthesis via two-electron oxygen reduction: From pH effect to device engineering. Chinese Chemical Letters, 2025, 36(5): 110277-. doi: 10.1016/j.cclet.2024.110277
10. [10]
  Zicong Yang , Guangshun Ran , Hui Song , Yukun Chang , Jinshu Wang , Hongyi Li . Synergistic Co Pd affection impart high overall water splitting efficiency to Pt/Ir-based electrocatalyst in acid. Chinese Chemical Letters, 2026, 37(3): 111370-. doi: 10.1016/j.cclet.2025.111370
11. [11]
  Liming Li , Yanchang Liu , Peng Kang , Donghui Feng , Yuguang Zhang , Hangxing Ren , Jianrong Zeng , He Zhu , Qiang Li , Xiaoya Cui . Scalable and rapid liquid synthesis of PtNi electrocatalyst for hydrogen evolution reaction. Chinese Chemical Letters, 2026, 37(2): 112022-. doi: 10.1016/j.cclet.2025.112022
12. [12]
  Jing Cao , Dezheng Zhang , Bianqing Ren , Ping Song , Weilin Xu . Mn incorporated RuO₂ nanocrystals as an efficient and stable bifunctional electrocatalyst for oxygen evolution reaction and hydrogen evolution reaction in acid and alkaline. Chinese Chemical Letters, 2024, 35(10): 109863-. doi: 10.1016/j.cclet.2024.109863
13. [13]
  Liang Ma , Zhou Li , Zhiqiang Jiang , Xiaofeng Wu , Shixin Chang , Sónia A. C. Carabineiro , Kangle Lv . Effect of precursors on the structure and photocatalytic performance of g-C3N4 for NO oxidation and CO2 reduction. Chinese Journal of Structural Chemistry, 2024, 43(11): 100416-100416. doi: 10.1016/j.cjsc.2024.100416
14. [14]
  Maomao Liu , Guizeng Liang , Ningce Zhang , Tao Li , Lipeng Diao , Ping Lu , Xiaoliang Zhao , Daohao Li , Dongjiang Yang . Electron-rich Ni2+ in Ni3S2 boosting electrocatalytic CO2 reduction to formate and syngas. Chinese Journal of Structural Chemistry, 2024, 43(8): 100359-100359. doi: 10.1016/j.cjsc.2024.100359
15. [15]
  Huiying Xu , Minghui Liang , Zhi Zhou , Hui Gao , Wei Yi . Application of Quantum Chemistry Computation and Visual Analysis in Teaching of Weak Interactions. University Chemistry, 2025, 40(3): 199-205. doi: 10.12461/PKU.DXHX202407011
16. [16]
  Xue Wu , Yupeng Liu , Bingzhe Wang , Lingyun Li , Zhenjian Li , Qingcheng Wang , Quansheng Cheng , Guichuan Xing , Songnan Qu . Rationally assembling different surface functionalized carbon dots for enhanced near-infrared tumor photothermal therapy. Acta Physico-Chimica Sinica, 2025, 41(9): 100109-0. doi: 10.1016/j.actphy.2025.100109
17. [17]
  Jiangqi Ning , Junhan Huang , Yuhang Liu , Yanlei Chen , Qing Niu , Qingqing Lin , Yajun He , Zheyuan Liu , Yan Yu , Liuyi Li . Alkyl-linked TiO2@COF heterostructure facilitating photocatalytic CO2 reduction by targeted electron transport. Chinese Journal of Structural Chemistry, 2024, 43(12): 100453-100453. doi: 10.1016/j.cjsc.2024.100453
18. [18]
  Na Lu , Tingting Pang , Xuedong Jing , Yongan Zhu , Linqun Yu , Sining Ben , Yuchan Song , Shiwen Du , Wei Lu , Zhenyi Zhang . Optimizing the Schottky Barrier in AuAg Alloy Decorated TiO2 Nanofibers to Enhance Hot-Electron-Induced CO2 Reduction. Chinese Journal of Structural Chemistry, 2025, 44(8): 100633-100633. doi: 10.1016/j.cjsc.2025.100633
19. [19]
  Muhammad Humayun , Mohamed Bououdina , Abbas Khan , Sajjad Ali , Chundong Wang . Designing single atom catalysts for exceptional electrochemical CO2 reduction. Chinese Journal of Structural Chemistry, 2024, 43(1): 100193-100193. doi: 10.1016/j.cjsc.2023.100193
20. [20]
  Xiuzheng Deng , Yi Ke , Jiawen Ding , Yingtang Zhou , Hui Huang , Qian Liang , Zhenhui Kang . Construction of ZnO@CDs@Co₃O₄ sandwich heterostructure with multi-interfacial electron-transfer toward enhanced photocatalytic CO₂ reduction. Chinese Chemical Letters, 2024, 35(4): 109064-. doi: 10.1016/j.cclet.2023.109064

Get Citation

PDF

XML

Metrics

PDF Downloads(0)
Abstract views(20)
HTML views(1)

通讯作者: 陈斌, bchen63@163.com

1.
沈阳化工大学材料科学与工程学院沈阳 110142

Mediating electron delocalization of surface palladium atoms by diethylamine ligand for efficient CO2 electroreduction

Metrics

通讯作者: 陈斌, bchen63@163.com

Mediating electron delocalization of surface palladium atoms by diethylamine ligand for efficient CO₂ electroreduction