Citation: Pu ZHANG, Youzhu YU, Yuhua GUO, Zhongyuan ZHOU. Syntheses and photocatalytic CO₂ reduction properties of heterometallic Ni/Sn and Co/Sn oxo clusters[J]. Chinese Journal of Inorganic Chemistry, ;2026, 42(5): 1039-1047. doi: 10.11862/CJIC.20250353 shu

Syntheses and photocatalytic CO₂ reduction properties of heterometallic Ni/Sn and Co/Sn oxo clusters

Pu ZHANG ¹ ,
Youzhu YU ^2,, ,
Yuhua GUO ² ,
Zhongyuan ZHOU ^2,,

1.
Department of Chemical and Material Engineering, Lyuliang University, Lüliang, Shanxi 033001, China
2.
School of Chemical and Environmental Engineering, Anyang Institute of Technology, Anyang, Henan 455000, China

Corresponding author: Youzhu YU, 119yyz@163.com Zhongyuan ZHOU, 20200038@ayit.edu.cn
Received Date: 25 November 2025
Revised Date: 16 January 2026

Figures(4)

In this work, by using diphenylphosphonic acid as ligand and butyltin hydroxide oxide as tin source, reacting with nickel acetate and cobalt acetate respectively, two hexanuclear tin oxo clusters formulated as [(n-BuSn)₄ Ni₂(μ₃-O)₂(μ₃-OH)₂(CH₃COO)₄(Ph₂PO₂)₆] (1) and [(n-BuSn)₄Co₂(μ₃-O)₂(μ₃-OH)₂(CH₃COO)₄(Ph₂PO₂)₆] (2) were solvothermally synthesized. Both 1 and 2 were characterized by infrared spectroscopy, elemental analysis, and single-crystal X-ray diffraction. Spectral experiments revealed that the two complexes have absorptions in the visible region. The optical band gaps for complexes 1 and 2 are 1.90 and 1.79 eV, respectively. Complexes 1 and 2 exhibited photocatalytic CO₂ reduction activity, and only CO was generated, with rates of 10.01 and 26.89 μmol·g^-1·h^-1, respectively. CCDC: 2505024, 1; 2505025, 2.
- transitional metal ions,
- tin oxo clusters,
- band gap,
- photocatalytic CO₂ reduction
1. [1]
  PRAKASH K, SENTHIL KUMAR P, PANDIARAJ S, SARAVANAKUMAR K, KARUTHAPANDIAN S. Controllable synthesis of SnO₂ photocatalyst with superior photocatalytic activity for the degradation of methylene blue dye solution[J]. J. Exp. Nanosci., 2016, 11(14): 1138-1155 doi: 10.1080/17458080.2016.1188222
2. [2]
  ZHENG L R, ZHENG Y H, CHEN C Q, ZHAN Y Y, LIN X Y, ZHENG Q, WEI K M, ZHU J F. Network structured SnO₂/ZnO heterojunction nanocatalyst with high photocatalytic activity[J]. Inorg. Chem., 2009, 48(5): 1819-1825 doi: 10.1021/ic802293p
3. [3]
  SUN C Y, YANG J K, XU M, CUI Y, REN W W, ZHANG J X, ZHAO H L, LIANG B. Recent intensification strategies of SnO₂-based photocatalysts: A review[J]. Chem. Eng. J., 2022, 427: 131564 doi: 10.1016/j.cej.2021.131564
4. [4]
  JUNAID M, SHARAF M, EI-MELIGY M, RIAZ M A, DAR M A, KHAN I U. Innovative approach to solar hydrogen generation using SnO₂ photocatalyst in water splitting[J]. J. Chin. Chem. Soc., 2025, 72(5): 488-497 doi: 10.1002/jccs.70009
5. [5]
  LIU C, HE J Q, SHEN L, HOU J H, ZHANG Y C. One-pot solvothermal synthesis of flower-like Zn²⁺-doped SnO₂ with superior photocatalytic activity[J]. J. Mol. Struct., 2025, 1330: 141500
6. [6]
  VINDHYA P, SURESH S, KAVITHA V. Biofabrication and characterisation of Ni-doped SnO₂ nanoparticles with enhanced cytotoxicity, antioxidant, antimicrobial and photocatalytic activities[J]. Appl. Organomet. Chem., 2025, 39(3): e7875 doi: 10.1002/aoc.7875
7. [7]
  SHABNA S, DHAS S S J, SHENBAGAVALLI V, NIXON R G S, BIJU C, SEBASTIAMMAL S, ASWATHAPPA S, ALMANSOUR A I. Preparation of S, Zn co-doped SnO₂ nanostructures and their insights into the structural, morphological, optical and photocatalytic activity[J]. Res. Chem. Intermed., 2025, 51(7): 3443-3466 doi: 10.1007/s11164-025-05608-2
8. [8]
  KARONNAN KOROTH S, ISLAM H, PAL U. VASUNDHARA M. Tailoring Co-loaded SnO₂ nanostructures as next-generation photocatalysts for efficient hydrogen evolution[J]. ACS Appl. Energy Mater., 2025, 8(21): 16082-16100 doi: 10.1021/acsaem.5c02588
9. [9]
  BISHT R, JOSHI G C, JOSHI C S. Investigation of the effect of Cu doping on dielectric and photocatalytic behaviour of SnO₂ nanoparticles[J]. J. Mater. Sci.‒Mater. Electron., 2025, 36(4): 235-241 doi: 10.1007/s10854-025-14288-y
10. [10]
  ZHU Y, ZHANG L, ZHANG J. Assembly of high-nuclearity Sn₂₆, Sn₃₄-oxo clusters: Solvent strategies and inorganic Sn incorporation[J]. Chem. Sci., 2019, 10(39): 9125-9129 doi: 10.1039/C9SC02503K
11. [11]
  ZHU Y, OLSEN M R, NYMAN M, ZHANG L, ZHANG J. Stabilizing gamma-alkyltin-oxo keggin ions by borate functionalization[J]. Inorg. Chem., 2019, 58(7): 4534-4539 doi: 10.1021/acs.inorgchem.9b00093
12. [12]
  LIU S B, XIAO J, LU X F, WANG J, WANG X, LOU X W. Efficient electrochemical reduction of CO₂ to HCOOH over sub-2 nm SnO₂ quantum wires with exposed grain boundaries[J]. Angew. Chem.‒Int. Edit., 2019, 58(25): 8499-8503 doi: 10.1002/anie.201903613
13. [13]
  ZHU Y, ZHANG J, ZHANG L. Sn₁₃-oxo clusters with an open hollow structural motif and decorated by different functional ligands[J]. Inorg. Chem., 2019, 58(23): 15692-15695 doi: 10.1021/acs.inorgchem.9b02474
14. [14]
  ZHU Y, LI Q H, LI D S, ZHANG, J, ZHANG L. Functional ligand directed assembly and electronic structure of Sn₁₈-oxo wheel nanoclusters[J]. Chem. Commun., 2021, 57(42): 5159-5162 doi: 10.1039/D1CC00651G
15. [15]
  GLOWACKI B, LUTTER M, SCHOLLMEYER D, HILLER W, JURKSCHAT K. Novel stannatrane N(CH₂CMe₂O)₂(CMe₂CH₂O)SnO-t-Bu and related oligonuclear tin(Ⅳ) oxoclusters. Two isomers in one crystal[J]. Inorg. Chem., 2016, 55(20): 10218-10228 doi: 10.1021/acs.inorgchem.6b01429
16. [16]
  WANG Q F, MA C L, HE G F, LI Z. Synthesis and characterization of new tin derivatives derived from 3, 5, 6-trichlorosalicylic acid: Cage, chain and ladder X-ray crystal structures[J]. Polyhedron, 2013, 49(1): 177-182 doi: 10.1016/j.poly.2012.09.057
17. [17]
  LIU F F, WANG, D, CHEN G H, QIAO Y, LUO F, ZHANG J, ZHANG L. Alkenyl-type ligands functionalized tin-lanthanide oxo nanoclusters as molecular lithography resists[J]. Sci. China Chem., 2023, 66(6): 1731-1736 doi: 10.1007/s11426-023-1598-3
18. [18]
  TIAN X J, YU Y Z, LU Q, ZHANG X M. Organic-inorganic high-valence Sn₁₈-oxo clusters: Direct utilization of an inorganic Sn(Ⅳ) source to improve the nuclearity and electrocatalytic CO₂ reduction properties[J]. Inorg. Chem., 2022, 61(16): 6037-6044 doi: 10.1021/acs.inorgchem.2c00038
19. [19]
  ZHU Y, WANG Z R, LI D J, ZHU Y D, LI Q H, LI D S, ZHANG L. Silver-templated γ-Keggin alkyltin-oxo cluster: Electronic structure and optical limiting effect[J]. Angew. Chem.‒Int. Edit., 2022, 61(27): e202202853 doi: 10.1002/anie.202202853
20. [20]
  WANG D, CHEN G H, WANG S T, ZHANG J, ZHANG L. Triethanolamine stabilized non-alkyl Sn₄Cd₄ and alkyl Sn₂Cd₁₂ oxo clusters with distinct electrocatalytic activities[J]. Chem. Commun., 2022, 58(30): 4759-4762 doi: 10.1039/D2CC00574C
21. [21]
  WANG D, YI X F, ZHANG L. Non-alkyl tin-oxo clusters as new-type patterning materials for nanolithography[J]. Sci. China Chem., 2022, 65(1): 114-119 doi: 10.1007/s11426-021-1092-2
22. [22]
  SUN X X, GUO Y H, YU Y Z. Crystal structure of bis(μ₃-diphenyl-phosphinato)-tetrakis(μ₂-diphenylphosphinato)-bis(diphenylphosphinato)-bis(μ₂-hydroxo)dicopper(Ⅱ)-ditin(Ⅳ), C₁₀₄H₁₀₀O₁₈P₈Cu₂Sn₂[J]. Z. Krist.‒New Cryst. Struct., 2023, 238(1): 123-125
23. [23]
  YU Y Z, ZHANG Y Y, GUO Y H, ZHOU Z Y, WU J, ZHANG S H, CHEN Y, DONG Y D. Syntheses and photoelectric properties of titanium oxo clusters assembled by salicylaldoxime and acetohydroxamic acid[J]. Chinese J. Inorg. Chem., 2023, 39(11): 2231-2239
24. [24]
  GUO Y H, YU Y Z, SHEN Y H, YANG L G, LIU N N, ZHOU Z Y, NIU Y S. “Three-in-one” structural-building-mode-based Ti₁₆-type titanium oxo cluster entirely protected by the ligands benzoate and salicylhydroxamate[J]. Inorg. Chem., 2022, 61: 8685-8693 doi: 10.1021/acs.inorgchem.2c00327
25. [25]
  YU Y Z, ZHANG Y R, GENG C H, SUN L, GUO Y, FENG Y R, WANG Y X, ZHANG X M. Precise and wide-ranged band-gap tuning of Ti₆-core-based titanium oxo clusters by the type and number of chromophore ligands[J]. Inorg. Chem., 2019, 58(24): 16785-16791 doi: 10.1021/acs.inorgchem.9b02951
26. [26]
  YU Y Z, ZHANG Y Y, GUO Y H, ZHOU Z Y, YANG L G, LI J L, FANG L Y, QIAO K K. Preparation, syntheses, structure-regulation and photoelectric properties of 2-pyridinecarbaldehyde oxime assembled titanium oxo clusters[J]. Chinese J. Inorg. Chem., 2022, 38(11): 2299-2307
27. [27]
  ESLAVA S, MCPARTLIN M, THOMSON R I, RAWSON J M, WRIGHT D S. Single-source materials for metal-doped titanium oxide: Syntheses, structures, and properties of a series of heterometallic transition-metal titanium oxo cages[J]. Inorg. Chem., 2010, 49(24): 11532-11540 doi: 10.1021/ic101687m
28. [28]
  ESLAVA S, GOODWILL B P, MCPARTLIN M, WRIGHT D S. Extending the family of titanium heterometallic-oxo-alkoxy cages[J]. Inorg. Chem., 2011, 50(12): 5655-5662 doi: 10.1021/ic200350j
29. [29]
  TAUC J. Absorption edge and internal electric fields in amorphous semiconductors[J]. Mater. Res. Bull., 1970, 5(8): 721-729 doi: 10.1016/0025-5408(70)90112-1
30. [30]
  CHEN W P, BAI K P, LV M T, NI S, HUANG C, YANG Q Y, ZHENG Y Z. Porous 3d-4f coordination clusters for selective visible-light photocatalytic CO₂ reduction to CO[J]. Angew. Chem.‒Int. Edit., 2025, 64(15): e202424805 doi: 10.1002/anie.202424805
1. [1]
  Dongdong Liu , Ziqi Tang , Haoyu Wang , Xinjie Li , Jingyang Li , Chao Zhu , Shan Ding , Yuan-sheng Cheng , Hui Zhang , Peipei Li , Ju Wu , Guozan Yuan . Rational design of ZnIn2S4-COF heterojunction to inhibit photogenerated carrier dynamics for enhanced photocatalytic CO2 reduction. Chinese Journal of Structural Chemistry, 2026, 45(1): 100762-100762. doi: 10.1016/j.cjsc.2025.100762
2. [2]
  Yi YANG , Shuang WANG , Wendan WANG , Limiao CHEN . Photocatalytic CO₂ reduction performance of Z-scheme Ag-Cu₂O/BiVO₄ photocatalyst. Chinese Journal of Inorganic Chemistry, 2024, 40(5): 895-906. doi: 10.11862/CJIC.20230434
3. [3]
  Tieping CAO , Yuejun LI , Dawei SUN . Surface plasmon resonance effect enhanced photocatalytic CO₂ reduction performance of S-scheme Bi₂S₃/TiO₂ heterojunction. Chinese Journal of Inorganic Chemistry, 2025, 41(5): 903-912. doi: 10.11862/CJIC.20240366
4. [4]
  Mohamed Saber Lassoued , Faizan Ahmad , Yanzhen Zheng . Film thickness effect on 2D lead-free hybrid double perovskite properties: Band gap, photocurrent and stability. Chinese Chemical Letters, 2025, 36(4): 110477-. doi: 10.1016/j.cclet.2024.110477
5. [5]
  Run-Han Li , Tian-Yi Dang , Wei Guan , Jiang Liu , Ya-Qian Lan , Zhong-Min Su . Evolution exploration and structure prediction of Keggin-type group IVB metal-oxo clusters. Chinese Chemical Letters, 2024, 35(5): 108805-. doi: 10.1016/j.cclet.2023.108805
6. [6]
  Hao-Nan Zhou , Lan-Yan Li , Hong-Bing Mo , Yi-Xin Li , Jun Yan , Chao Liu . Ligand-engineered octanuclear bismuth-oxo clusters with exposed active sites for enhanced CO₂-to-HCOOH electroreduction. Chinese Chemical Letters, 2025, 36(10): 111269-. doi: 10.1016/j.cclet.2025.111269
7. [7]
  Xueyang Zhao , Bangwei Deng , Hongtao Xie , Yizhao Li , Qingqing Ye , Fan Dong . Recent process in developing advanced heterogeneous diatomic-site metal catalysts for electrochemical CO₂ reduction. Chinese Chemical Letters, 2024, 35(7): 109139-. doi: 10.1016/j.cclet.2023.109139
8. [8]
  Tinghui Yang , Min Kuang , Jianping Yang . Mesoporous CuCe dual-metal catalysts for efficient electrochemical reduction of CO2 to methane. Chinese Journal of Structural Chemistry, 2024, 43(8): 100350-100350. doi: 10.1016/j.cjsc.2024.100350
9. [9]
  Ruolin CHENG , Yue WANG , Fei YANG , Huagen LIANG , Shijian LU . Application of metal-organic frameworks (MOFs) in photocatalytic CO₂ cycloaddition reaction: A mini review. Chinese Journal of Inorganic Chemistry, 2025, 41(12): 2429-2440. doi: 10.11862/CJIC.20250242
10. [10]
  Yidan Mao , Bingyu Li , Shuailing Ma , Siwen Cui , Zihan Zhang , Pinwen Zhu , Kongsheng Qi , Xiaodong Li , Weiwei Dong , Wei Luo , Rajeev Ahuja , Dexin Yang , Tian Cui . Metal diborides as robust and highly stable electrodes for efficient electrocatalytic reduction of CO₂ to CO in ionic liquid-based electrolytes. Chinese Chemical Letters, 2026, 37(4): 111675-. doi: 10.1016/j.cclet.2025.111675
11. [11]
  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
12. [12]
  Jiaqi Ma , Lan Li , Yiming Zhang , Jinjie Qian , Xusheng Wang . Covalent organic frameworks: Synthesis, structures, characterizations and progress of photocatalytic reduction of CO2. Chinese Journal of Structural Chemistry, 2024, 43(12): 100466-100466. doi: 10.1016/j.cjsc.2024.100466
13. [13]
  Jingtai Bi , Yupeng Cheng , Mengmeng Sun , Xiaofu Guo , Shizhao Wang , Yingying Zhao . Efficient and selective photocatalytic nitrite reduction to N₂ through CO₂ anion radical by eco-friendly tartaric acid activation. Chinese Chemical Letters, 2024, 35(11): 109639-. doi: 10.1016/j.cclet.2024.109639
14. [14]
  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
15. [15]
  Hui Li , Chunlang Gao , Guo Yang , Lu Xia , Wulyu Jiang , Cheng Wu , Kaiwen Wang , Yingtang Zhou , Xiaodong Han . Enhanced photocatalytic CO₂ reduction of Bi₂WO₆-BiOCl heterostructure with coherent interface for charge utilization. Chinese Chemical Letters, 2025, 36(9): 110547-. doi: 10.1016/j.cclet.2024.110547
16. [16]
  Hai-Ling Wang , Zhong-Hong Zhu , Hua-Hong Zou . Structure and assembly mechanism of high-nuclear lanthanide-oxo clusters. Chinese Journal of Structural Chemistry, 2024, 43(9): 100372-100372. doi: 10.1016/j.cjsc.2024.100372
17. [17]
  Xingxing Jiang , Yuxin Zhao , Yan Kong , Jianju Sun , Shangzhao Feng , Xin Lu , Qi Hu , Hengpan Yang , Chuanxin He . Support effect and confinement effect of porous carbon loaded tin dioxide nanoparticles in high-performance CO₂ electroreduction towards formate. Chinese Chemical Letters, 2025, 36(1): 109555-. doi: 10.1016/j.cclet.2024.109555
18. [18]
  Xiaoxia WANG , Ya'nan GUO , Feng SU , Chun HAN , Long SUN . Synthesis, structure, and electrocatalytic oxygen reduction reaction properties of metal antimony-based chalcogenide clusters. Chinese Journal of Inorganic Chemistry, 2024, 40(6): 1201-1208. doi: 10.11862/CJIC.20230478
19. [19]
  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
20. [20]
  Jingtao Bi , Yupeng Cheng , Mengmeng Sun , Xiaofu Guo , Shizhao Wang , Yingying Zhao . Corrigendum to “Efficient and selective photocatalytic nitrite reduction to N₂ through CO₂ anion radical by eco-friendly tartaric acid activation” [Chinese Chemical Letters 35 (2024) 109639]. Chinese Chemical Letters, 2025, 36(7): 110867-. doi: 10.1016/j.cclet.2025.110867

Get Citation

PDF

XML

Metrics

PDF Downloads(0)
Abstract views(53)
HTML views(12)

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

Syntheses and photocatalytic CO2 reduction properties of heterometallic Ni/Sn and Co/Sn oxo clusters

Metrics

通讯作者: 陈斌, bchen63@163.com

Syntheses and photocatalytic CO₂ reduction properties of heterometallic Ni/Sn and Co/Sn oxo clusters