Citation: Anqun LAI, Qiaoyu WU, Qingqing LIANG, Qiyong LI, Guowen DONG, Yongjie DING, Jia′nan CHEN, Qing YAN, Zhonghua PAN, Wangchuan XIAO. Electrocatalytic water oxidation properties of Nd-Co polynuclear complexes[J]. Chinese Journal of Inorganic Chemistry, ;2025, 41(12): 2527-2535. doi: 10.11862/CJIC.20250151 shu

Electrocatalytic water oxidation properties of Nd-Co polynuclear complexes

Anqun LAI ^{1, 2} ,
Qiaoyu WU ¹ ,
Qingqing LIANG ¹ ,
Qiyong LI ¹ ,
Guowen DONG ¹ ,
Yongjie DING ¹ ,
Jia′nan CHEN ³ ,
Qing YAN ⁴ ,
Zhonghua PAN ^{1, 5,,} ,
Wangchuan XIAO ^{1, 2, 5,,}

1.
School of Resources and Chemical Engineering, Sanming University, Sanming, Fujian 365004, China
2.
College of Chemistry and Materials Science, Fujian Normal University, Fuzhou, Fujian 350007, China
3.
College of Chemistry and Chemical Engineering, Xiamen University, Xiamen, Fujian 361005, China
4.
School of Biological and Chemical Engineering, NingboTech University, Ningbo, Zhejiang 315100, China
5.
Insitute of Fluorochemical Industry, Sanming, Fujian 365004, China

Corresponding author: Zhonghua PAN, zhpan@fjsmu.edu.cn Wangchuan XIAO, xwc@fjsmu.edu.cn
Received Date: 1 May 2025
Revised Date: 20 September 2025

Figures(9)

A heterometallic polynuclear complex, [NdCo₆(py)₆(aib)₆(μ₃-O)₃(NO₃)₃]·H₂O (NdCo₆-py), was synthesized through a layered diffusion method utilizing 2-aminoisobutyric acid (Haib) and pyridine (py) as coordinating ligands. Single-crystal X-ray diffraction reveals its unique architecture featuring a trigonal prismatic [NdCo₆] core, where the central Nd³⁺ ion is encapsulated between two parallel, nearly equilateral Co₃ triangles. This cage-like structure stabilizes the Nd³⁺ center while exposing multiple metal sites at the periphery. Electrocatalytic studies demonstrate that NdCo₆-py exhibits remarkable catalytic activity towards the oxygen evolution reaction (OER), achieving a high turnover frequency (TOF) of 279 s⁻¹ and Faradaic efficiency of 92.6% at 1.60 V (vs NHE). This exceptional electrocatalytic performance is attributed to the readily accessible bimetallic synergistic active sites within the cluster framework. These sites facilitate the O—O bond formation step through a cooperative mechanism, effectively mitigating the formation of high-valent metal intermediates and consequently lowering the reaction overpotential. These findings provide compelling evidence for the efficacy of the polymetallic synergistic catalysis strategy in modulating the O—O bond formation pathway.
- rare earth-transition metal polynuclear complexes,
- molecular catalysts,
- electrocatalysis,
- synergistic catalysis,
- water oxidation
1. [1]
  WULF C, HAASE M, BAUMANN M, ZAPP P. Weighting factor elicitation for sustainability assessment of energy technologies[J]. Sustain. Energ. Fuels, 2023,7(3):832-847. doi: 10.1039/D2SE01170K
2. [2]
  FU H, WU Y Q, GUO Y H, SAKURAI T, ZHANG Q Q, LIU Y Y, ZHENG Z K, CHENG H F, WANG Z Y, HUANG B B, WANG Q, DOMEN K, WANG P. A scalable solar-driven photocatalytic system for separated H₂ and O₂ production from water[J]. Nat. Commun., 2025,16(1)990. doi: 10.1038/s41467-025-56314-x
3. [3]
  ODENWELLER A, UECKERDT F. An adjusted strategy is needed to ground green hydrogen expectations in reality[J]. Nat. Energy, 2025,10(1):19-20.
4. [4]
  LIN M S, NIE Q B, CHEN J N, LIU Z Y, WU Q Y, LIU X F, LIU C, PAN Z H, XIAO W C, LUO G G. Synthesis, photophysics and photosensitizing hydrogen evolution of a near-infrared heavy-atom-free sensitizer[J]. New J. Chem., 2025,49(18):7647-7654. doi: 10.1039/D5NJ00537J
5. [5]
  YOU B, SUN Y J. Innovative strategies for electrocatalytic water splitting[J]. Accounts Chem. Res., 2018,51(7):1571-1580. doi: 10.1021/acs.accounts.8b00002
6. [6]
  BERARDI S, DROUET S, FRANCàS L, GIMBERT-SURIñACH C, GUTTENTAG M, RICHMOND C, STOLL T, LLOBET A. Molecular artificial photosynthesis[J]. Chem. Soc. Rev., 2014,43(22):7501-7519. doi: 10.1039/C3CS60405E
7. [7]
  HU C L, ZHANG L, GONG J L. Recent progress made in the mechanism comprehension and design of electrocatalysts for alkaline water splitting[J]. Energy Environ. Sci., 2019,12(9):2620-2645. doi: 10.1039/C9EE01202H
8. [8]
  YANG S J, HAN J X, ZHANG W. Proton-coupled electron transfer in electrocatalytic water splitting[J]. Chem. ‒Eur. J., 2023,29(69)e202302770. doi: 10.1002/chem.202302770
9. [9]
  UMENA Y, KAWAKAMI K, SHEN J R, KAMIYA N. Crystal structure of oxygen-evolving photosystem Ⅱ at a resolution of 1.9 Å[J]. Nature, 2011,473(7345):55-60. doi: 10.1038/nature09913
10. [10]
  KANADY J S, TSUI E Y, DAY M W, AGAPIE T. A synthetic model of the Mn₃Ca subsite of the oxygen-evolving complex in photosystem Ⅱ[J]. Science, 2011,333(6043):733-736. doi: 10.1126/science.1206036
11. [11]
  LIU X, CAI X, ZHU Y. Catalysis synergism by atomically precise bimetallic nanoclusters doped with heteroatoms[J]. Accounts Chem. Res., 2023,56(12):1528-1538. doi: 10.1021/acs.accounts.3c00118
12. [12]
  NOLL N, KRAUSE A M, BEUERLE F, WÜRTHNER F. Enzyme-like water preorganization in a synthetic molecular cleft for homogeneous water oxidation catalysis[J]. Nat. Catal., 2022,5(10):867-877. doi: 10.1038/s41929-022-00843-x
13. [13]
  DEN BOER D, HETTERSCHEID D G H. Design principles for homogeneous water oxidation catalysts based on first-row transition metals[J]. Curr. Opin. Electrochem., 2022,35101064. doi: 10.1016/j.coelec.2022.101064
14. [14]
  HAN L, DONG S J, WANG E K. Transition-metal (Co, Ni, and Fe)-based electrocatalysts for the water oxidation reaction[J]. Adv. Mater., 2016,28(42):9266-9291. doi: 10.1002/adma.201602270
15. [15]
  PEI G X, ZHANG L L, SUN X Y. Recent advances of bimetallic nanoclusters with atomic precision for catalytic applications[J]. Coord. Chem. Rev., 2024,506215692. doi: 10.1016/j.ccr.2024.215692
16. [16]
  LI S, LI N N, DONG X Y, ZANG S Q, MAK T C W. Chemical flexibility of atomically precise metal clusters[J]. Chem. Rev., 2024,124(11):7262-7378. doi: 10.1021/acs.chemrev.3c00896
17. [17]
  BENCINI A, BENELLI C, CANESCHI A, CARLIN R L, DEI A, GATTESCHI D. Crystal and molecular structure of and magnetic coupling in two complexes containing gadolinium(Ⅲ) and copper(Ⅱ) ions[J]. J. Am. Chem. Soc., 1985,107(26):8128-8136. doi: 10.1021/ja00312a054
18. [18]
  ZHENG B Z, FAN J Y, CHEN B, QIN X, WANG J, WANG F, DENG R R, LIU X G. Rare-earth doping in nanostructured inorganic materials[J]. Chem. Rev., 2022,122(6):5519-5603. doi: 10.1021/acs.chemrev.1c00644
19. [19]
  QI M Q, DU M H, KONG X J, LONG L S, ZHENG L S. Electrospray ionization mass spectrometry insights into the assembly of lanthanide-containing clusters[J]. Accounts Chem. Res., 2025,58(12):1867-1877. doi: 10.1021/acs.accounts.5c00151
20. [20]
  CHEN W P, LIAO P Q, JIN P B, ZHANG L, LING B K, WANG S C, CHAN Y T, CHEN X M, ZHENG Y Z. The gigantic {Ni₃₆Gd₁₀₂} hexagon: A sulfate-templated "star-of-david" for photocatalytic CO₂ reduction and magnetic cooling[J]. J. Am. Chem. Soc., 2020,142(10):4663-4670. doi: 10.1021/jacs.9b11543
21. [21]
  JIA T, CHENG P M, ZHANG M X, LIU W D, LI C Y, SU H F, LONG L S, ZHENG L S, KONG X J. Ln^Ⅲ/Cu^Ⅰ bimetallic nanoclusters with enhanced NIR-Ⅱ luminescence[J]. J. Am. Chem. Soc., 2024,146(42):28618-28623. doi: 10.1021/jacs.4c09447
22. [22]
  DU M H, ZHENG X Y, KONG X J, LONG L S, ZHENG L S. Synthetic protocol for assembling giant heterometallic hydroxide clusters from building blocks: Rational design and efficient synthesis[J]. Matter, 2020,3(4):1334-1349. doi: 10.1016/j.matt.2020.06.020
23. [23]
  PAN Z H, WENG Z Z, KONG X J, LONG L S, ZHENG L S. Lanthanide-containing clusters for catalytic water splitting and CO₂ conversion[J]. Coord. Chem. Rev., 2022,457214419. doi: 10.1016/j.ccr.2022.214419
24. [24]
  LAN T X, GAO W S, CHEN C N, WANG H S, WANG M, FAN Y H. Two tetranuclear 3d-4f heterometal complexes Mn₂Ln₂ (Ln=Dy, Gd): Synthesis, structure, magnetism, and electrocatalytic reactivity for water oxidation[J]. New J. Chem., 2018,42(8):5798-5805. doi: 10.1039/C8NJ00149A
25. [25]
  EVANGELISTI F, GÜTTINGER R, MORÉ R, LUBER S, PATZKE G R. Closer to photosystem Ⅱ: A Co₄O₄ cubane catalyst with flexible ligand architecture[J]. J. Am. Chem. Soc., 2013,135(50):18734-18737. doi: 10.1021/ja4098302
26. [26]
  CHEN R, CHEN C L, DU M H, WANG X, WANG C, LONG L S, KONG X J, ZHENG L S. Soluble lanthanide-transition-metal clusters Ln₃₆Co₁₂ as effective molecular electrocatalysts for water oxidation[J]. Chem. Commun., 2021,57(29):3611-3614. doi: 10.1039/D0CC08132A
27. [27]
  CHEN J N, PAN Z H, QIU Q H, WANG C, LONG L S, ZHENG L S, KONG X J. Soluble Gd₆Cu₂₄ clusters: Effective molecular electrocatalysts for water oxidation[J]. Chem. Sci., 2024,15(2):511-515. doi: 10.1039/D3SC05849B
28. [28]
  JIANG X, LI J, YANG B, WEI X Z, DONG B W, KAO Y, HUANG M Y, TUNG C H, WU L Z. A bio-inspired Cu₄O₄ cubane: Effective molecular catalysts for electrocatalytic water oxidation in aqueous solution[J]. Angew. Chem. ‒Int. Edit., 2018,57(26):7850-7854. doi: 10.1002/anie.201803944
29. [29]
  GARRIDO-BARROS P, FUNES-ARDOIZ I, DROUET S, BENET-BUCHHOLZ J, MASERAS F, LLOBET A. Redox non-innocent ligand controls water oxidation overpotential in a new family of mononuclear Cu-based efficient catalysts[J]. J. Am. Chem. Soc., 2015,137(21):6758-6761. doi: 10.1021/jacs.5b03977
30. [30]
  LU C, DU J L, SU X J, ZHANG M T, XU X X, MEYER T J, CHEN Z F. Cu(Ⅱ) aliphatic diamine complexes for both heterogeneous and homogeneous water oxidation catalysis in basic and neutral solutions[J]. ACS Catal., 2016,6(1):77-83. doi: 10.1021/acscatal.5b02173
31. [31]
  CHEN J N, PAN Z H, SUN F L, WU P X, ZHENG S T, ZHUANG G L, LONG L S, ZHENG L S, KONG X J. Tuning electrocatalytic water oxidation activity: Insights from the active-site distance in LnCu₆ clusters[J]. Small, 2024,20(32)2401044. doi: 10.1002/smll.202401044
32. [32]
  XIAO W C, NIE Q B, LUO G G. Secondary hierarchical complexity in double-stranded cluster helicates covered by NNNNN type pincer ligands[J]. Dalton Trans., 2023,52(19):6239-6243. doi: 10.1039/D3DT00912B
33. [33]
  CHEN J N, PAN Z H, SUN F L, LI J P, ZHUANG G L, LONG L S, ZHENG L S, KONG X J. Synergistic mechanisms of oxygen evolution reaction in atomically precise LaCo₆ clusters with distinct geometries[J]. Sci. China Chem., 2025,68(5):1832-1836. doi: 10.1007/s11426-024-2570-y
34. [34]
  CHEN F F, WANG N, LEI H T, GUO D Y, LIU H F, ZHANG Z Y, ZHANG W, LAI W Z, CAO R. Electrocatalytic water oxidation by a water-soluble copper(Ⅱ) complex with a copper-bound carbonate group acting as a potential proton shuttle[J]. Inorg. Chem., 2017,56(21):13368-13375. doi: 10.1021/acs.inorgchem.7b02125
35. [35]
  CERONI P, CREDI A, VENTURI M. Electrochemical methods//SCHALLEY C A. Analytical methods in supramolecular chemistry: Vol. 2[M]. 2nd ed. Weinheim: Wiley-VCJ, 2012: 371-457
36. [36]
  LAVIRON E. General expression of the linear potential sweep voltammogram in the case of diffusionless electrochemical systems[J]. J. Electroanal. Chem., 1979,101(1):19-28. doi: 10.1016/S0022-0728(79)80075-3
37. [37]
  GHOSH T, MAAYAN G. Efficient homogeneous electrocatalytic water oxidation by a manganese cluster with an overpotential of only 74 mV[J]. Angew. Chem. ‒Int. Edit., 2019,58(9):2785-2790. doi: 10.1002/anie.201813895
38. [38]
  CHEN Q F, XIAN K L, ZHANG H T, SU X J, LIAO R Z, ZHANG M T. Pivotal role of geometry regulation on O—O bond formation mechanism of bimetallic water oxidation catalysts[J]. Angew. Chem. ‒Int. Edit., 2024,63(9)e202317514. doi: 10.1002/anie.202317514
39. [39]
  YAN Q, LIU Y, ZHAO Y, ZHOU X, YUAN W. Molten salt-mediated electrosynthesis of MoS₂ nanosheet-supported Rh nanoclusters for highly efficient electrocatalytic hydrogen evolution[J]. Chem. Commun., 2025,61(18):3700-3703. doi: 10.1039/D4CC06224H
40. [40]
  DU X, ZHANG J, ZHANG M, WEI H, LIN X, GUO W, ZHANG P, LUO Z H. Deciphering the synergistic role of chemisorbed phosphate on FeOOH for high-efficiency overall water splitting[J]. Green Chem., 2025,27:7380-7388. doi: 10.1039/D5GC01624J
41. [41]
  ZHOU X Y, ZHANG J J, ZHANG M Y, DU X Q, BAO W W, HAN J, LIN X, ZHANG P F, LUO Z H. Active site reconstruction of a metal hydroxide/metal molybdate heterogeneous interface enhances electrochemical water oxidation[J]. Inorg. Chem. Front., 2025,12(19):5819-5829. doi: 10.1039/D5QI00418G
42. [42]
  SCHULZE M, KUNZ V, FRISCHMANN P D, WÜRTHNER F. A supramolecular ruthenium macrocycle with high catalytic activity for water oxidation that mechanistically mimics photosystem Ⅱ[J]. Nat. Chem., 2016,8(6):576-583. doi: 10.1038/nchem.2503
43. [43]
  CHEN Q F, CHENG Z Y, LIAO R Z, ZHANG M T. Bioinspired trinuclear copper catalyst for water oxidation with a turnover frequency up to 20 000 s^-1[J]. J. Am. Chem. Soc., 2021,143(47):19761-19768. doi: 10.1021/jacs.1c08078
44. [44]
  SU X J, GAO M, JIAO L, LIAO R Z, SIEGBAHN P E M, CHENG J P, ZHANG M T. Electrocatalytic water oxidation by a dinuclear copper complex in a neutral aqueous solution[J]. Angew. Chem. ‒Int. Edit., 2015,54(16):4909-4914. doi: 10.1002/anie.201411625
1. [1]
  Qiangqiang SUN , Pengcheng ZHAO , Ruoyu WU , Baoyue CAO . Multistage microporous bifunctional catalyst constructed by P-doped nickel-based sulfide ultra-thin nanosheets for energy-efficient hydrogen production from water electrolysis. Chinese Journal of Inorganic Chemistry, 2024, 40(6): 1151-1161. doi: 10.11862/CJIC.20230454
2. [2]
  Ye Wang , Ruixiang Ge , Xiang Liu , Jing Li , Haohong Duan . An Anion Leaching Strategy towards Metal Oxyhydroxides Synthesis for Electrocatalytic Oxidation of Glycerol. Acta Physico-Chimica Sinica, 2024, 40(7): 2307019-0. doi: 10.3866/PKU.WHXB202307019
3. [3]
  Shihui Shi , Haoyu Li , Shaojie Han , Yifan Yao , Siqi Liu . Regioselectively Synthesis of Halogenated Arenes via Self-Assembly and Synergistic Catalysis Strategy. University Chemistry, 2024, 39(5): 336-344. doi: 10.3866/PKU.DXHX202312002
4. [4]
  Yan Kong , Wei Wei , Lekai Xu , Chen Chen . Electrochemical Synthesis of Organonitrogen Compounds from N-integrated CO₂ Reduction Reaction. Acta Physico-Chimica Sinica, 2024, 40(8): 2307049-0. doi: 10.3866/PKU.WHXB202307049
5. [5]
  Wentao Xu , Xuyan Mo , Yang Zhou , Zuxian Weng , Kunling Mo , Yanhua Wu , Xinlin Jiang , Dan Li , Tangqi Lan , Huan Wen , Fuqin Zheng , Youjun Fan , Wei Chen . Bimetal Leaching Induced Reconstruction of Water Oxidation Electrocatalyst for Enhanced Activity and Stability. Acta Physico-Chimica Sinica, 2024, 40(8): 2308003-0. doi: 10.3866/PKU.WHXB202308003
6. [6]
  Dingwen CHEN , Siheng YANG , Haiyan FU , Hua CHEN , Xueli ZHENG , Weichao XUE , Jiaqi XU , Ruixiang LI . NiOOH-mediated synthesis of gold nanoaggregates for electrocatalytic performance for selective oxidation of glycerol to glycolate. Chinese Journal of Inorganic Chemistry, 2025, 41(11): 2317-2326. doi: 10.11862/CJIC.20250053
7. [7]
  Xinlong XU , Chunxue JING , Yuzhen CHEN . Bimetallic MOF-74 and derivatives: Fabrication and efficient electrocatalytic biomass conversion. Chinese Journal of Inorganic Chemistry, 2025, 41(8): 1545-1554. doi: 10.11862/CJIC.20250046
8. [8]
  Lu Zhuoran , Li Shengkai , Lu Yuxuan , Wang Shuangyin , Zou Yuqin . Cleavage of C―C Bonds for Biomass Upgrading on Transition Metal Electrocatalysts. Acta Physico-Chimica Sinica, 2024, 40(4): 2306003-0. doi: 10.3866/PKU.WHXB202306003
9. [9]
  Qing Li , Guangxun Zhang , Yuxia Xu , Yangyang Sun , Huan Pang . P-Regulated Hierarchical Structure Ni₂P Assemblies toward Efficient Electrochemical Urea Oxidation. Acta Physico-Chimica Sinica, 2024, 40(9): 2308045-0. doi: 10.3866/PKU.WHXB202308045
10. [10]
  Tao Wang , Qin Dong , Cunpu Li , Zidong Wei . Sulfur Cathode Electrocatalysis in Lithium-Sulfur Batteries: A Comprehensive Understanding. Acta Physico-Chimica Sinica, 2024, 40(2): 2303061-0. doi: 10.3866/PKU.WHXB202303061
11. [11]
  Tongtong Zhao , Yan Wang , Shiyue Qin , Liang Xu , Zhenhua Li . New Experiment Development: Upgrading and Regeneration of Discarded PET Plastic through Electrocatalysis. University Chemistry, 2024, 39(3): 308-315. doi: 10.3866/PKU.DXHX202309003
12. [12]
  Jiajie Li , Xiaocong Ma , Jufang Zheng , Qiang Wan , Xiaoshun Zhou , Yahao Wang . Recent Advances in In-Situ Raman Spectroscopy for Investigating Electrocatalytic Organic Reaction Mechanisms. University Chemistry, 2025, 40(4): 261-276. doi: 10.12461/PKU.DXHX202406117
13. [13]
  Jianchun Wang , Ruyu Xie . The Fantastical Dance of Miss Electron: Contra-Thermodynamic Electrocatalytic Reactions. University Chemistry, 2025, 40(4): 331-339. doi: 10.12461/PKU.DXHX202406082
14. [14]
  Xueting Cao , Shuangshuang Cha , Ming Gong . Interfacial Electrical Double Layer in Electrocatalytic Reactions: Fundamentals, Characterizations and Applications. Acta Physico-Chimica Sinica, 2025, 41(5): 100041-0. doi: 10.1016/j.actphy.2024.100041
15. [15]
  Xinyi Zhang , Kai Ren , Yanning Liu , Zhenyi Gu , Zhixiong Huang , Shuohang Zheng , Xiaotong Wang , Jinzhi Guo , Igor V. Zatovsky , Junming Cao , Xinglong Wu . Progress on Entropy Production Engineering for Electrochemical Catalysis. Acta Physico-Chimica Sinica, 2024, 40(7): 2307057-0. doi: 10.3866/PKU.WHXB202307057
16. [16]
  Fangfang WANG , Jiaqi CHEN , Weiyin SUN . CuBi@Cu-MOF composite catalysts for electrocatalytic CO₂ reduction to HCOOH. Chinese Journal of Inorganic Chemistry, 2025, 41(1): 97-104. doi: 10.11862/CJIC.20240350
17. [17]
  Jinyi Sun , Lin Ma , Yanjie Xi , Jing Wang . Preparation and Electrocatalytic Nitrogen Reduction Performance Study of Vanadium Nitride@Nitrogen-Doped Carbon Composite Nanomaterials: A Recommended Comprehensive Chemistry Experiment. University Chemistry, 2024, 39(4): 184-191. doi: 10.3866/PKU.DXHX202310094
18. [18]
  Xiting Zhou , Zhipeng Han , Xinlei Zhang , Shixuan Zhu , Cheng Che , Liang Xu , Zhenyu Sun , Leiduan Hao , Zhiyu Yang . Dual Modulation via Ag-Doped CuO Catalyst and Iodide-Containing Electrolyte for Enhanced Electrocatalytic CO₂ Reduction to Multi-Carbon Products: A Comprehensive Chemistry Experiment. University Chemistry, 2025, 40(7): 336-344. doi: 10.12461/PKU.DXHX202412070
19. [19]
  Xue Dong , Xiaofu Sun , Shuaiqiang Jia , Shitao Han , Dawei Zhou , Ting Yao , Min Wang , Minghui Fang , Haihong Wu , Buxing Han . Electrochemical CO₂ Reduction to C₂₊ Products with Ampere-Level Current on Carbon-Modified Copper Catalysts. Acta Physico-Chimica Sinica, 2025, 41(3): 100024-0. doi: 10.3866/PKU.WHXB202404012
20. [20]
  Jiaxin Su , Jiaqi Zhang , Shuming Chai , Yankun Wang , Sibo Wang , Yuanxing Fang . Optimizing Poly(heptazine imide) Photoanodes Using Binary Molten Salt Synthesis for Water Oxidation Reaction. Acta Physico-Chimica Sinica, 2024, 40(12): 2408012-0. doi: 10.3866/PKU.WHXB202408012

Get Citation

PDF

XML

Metrics

PDF Downloads(0)
Abstract views(116)
HTML views(16)

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