Citation: Pu ZHANG, Youzhu YU, Yuhua GUO, Zhongyuan ZHOU. Synthesis and photocatalytic CO₂ reduction properties of heterometallic salicylate Mn/Ti clusters[J]. Chinese Journal of Inorganic Chemistry, ;2026, 42(8): 1723-1732. doi: 10.11862/CJIC.20260103 shu

Synthesis and photocatalytic CO₂ reduction properties of heterometallic salicylate Mn/Ti 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.
College 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: 30 March 2026
Revised Date: 22 June 2026

Figures(6)

A heterometallic Mn/Ti cluster formulated as [Ti₃Mn₂(Sal)₈(Phen)(CH₃CN)(H₂O)] (1) was solvothermally synthesized via the reaction of manganese acetate with a titanate precursor, using salicylic acid (H₂Sal) and 1, 10-phenanthroline (Phen) as organic ligands. By carefully tuning the reaction parameters and eliminating Phen from the reaction system, a structurally distinct heterometallic Mn/Ti cluster, [Ti₄Mn₄(Sal)₁₂(CH₃CN)₂]·(CH₃CN)₄ (2), was further isolated. The molecular structures of both complexes 1 and 2 were unambiguously established by elemental analysis, Fourier-transform infrared (FTIR) spectra, and single-crystal X-ray diffraction. Spectroscopic measurements demonstrated that both complexes feature prominent light absorption in the visible region, with the calculated optical band gaps of 1.93 eV for complex 1 and 2.15 eV for complex 2, respectively. Photocatalytic investigations revealed that complexes 1 and 2 exhibited efficient catalytic activity toward CO₂ reduction, affording CO as the exclusive carbon-containing product, with corresponding CO evolution rates of 7.21 and 14.39 μmol·g^-1·h^-1, respectively.
- titanium clusters,
- manganese,
- band gap,
- photocatalytic CO₂ reduction
1. [1]
  FUJISHIMA A, HONDA K. Electrochemical photolysis of water at a semiconductor electrode[J]. Nature, 1972, 238(5358): 37-38 doi: 10.1038/238037a0
2. [2]
  WANG J Q, WANG Z H, WANG W, WANG Y, HU X L, LIU J X, GONG X Z, MIAO W L, DING L L, LI X B, TANG J G. Synthesis, modification and application of titanium dioxide nanoparticles: A review[J]. Nanoscale, 2022, 14(18): 6709-6734 doi: 10.1039/D1NR08349J
3. [3]
  GUPTA S M. TRIPATHI M. A review of TiO₂ nanoparticles[J]. Chin. Sci. Bull., 2011, 56(16): 1639-1657 doi: 10.1007/s11434-011-4476-1
4. [4]
  LAN Y C, XIE Y Z, CHEN J X, HU Z F, CUI D H. Selective photocatalytic CO₂ reduction on copper-titanium dioxide: A study of the relationship between CO production and H₂ suppression[J]. Chem. Commun., 2019, 55(56): 8068-8071 doi: 10.1039/C9CC02891A
5. [5]
  LIU B, CHEN H M, LIU C, ANDREWS S C, HAHN C, YANG P. Large-scale synthesis of transition-metal-doped TiO₂ nanowires with controllable overpotential[J]. J Am. Chem. Soc., 2013, 135(27): 9995-9998 doi: 10.1021/ja403761s
6. [6]
  ZHANG D N, CHEN J H, XIANG Q J, LI Y X, LIU M Z, LIAO Y L. Transition-metal-ion (Fe, Co, Cr, Mn, etc.) doping of TiO₂ nanotubes: A general approach[J]. Inorg. Chem., 2019, 58(19): 12511-12515 doi: 10.1021/acs.inorgchem.9b01889
7. [7]
  NAIR P S, RAHMAN H, JOSEPH J A, NORBERT A, SHAJI S, TRIPATHI S, JHA S N, PHILIP R R. Band gap engineering of TiO₂ by Mn doping and the effect of p-TNT: Mn/n-MnO₂ heterojunction on photocatalytic applications[J]. Appl. Phys. A‒Mater. Sci. Process., 2022, 128(12): 1089 doi: 10.1007/s00339-022-06246-w
8. [8]
  FANG W H, ZHANG L, ZHANG J. A 3.6 nm Ti₅₂-oxo nanocluster with precise atomic structure[J]. J. Am. Chem. Soc., 2016, 138(24): 7480-7483 doi: 10.1021/jacs.6b03489
9. [9]
  GAO M Y, ZHANG L, ZHANG J. Preparation and properties of polyoxo-titanium clusters[J]. Chin. Sci. Bull., 2018, 63(26): 2731-2744
10. [10]
  FAN X, YUAN F R, LI D J, CHEN S, CHENG Z B, ZHANG Z J, XIANG S C, ZANG S Q, ZHANG J, ZHANG L. Threefold collaborative stabilization of Ag₁₄-nanorods by hydrophobic Ti₁₆-oxo clusters and alkynes: Designable assembly and solid-state optical-limiting application[J]. Angew. Chem.‒Int. Edit., 2021, 60(23): 12949-12954 doi: 10.1002/anie.202101664
11. [11]
  FU H, ZHOU S Y, FAN X, ZHANG L, ZHANG J. Assembly and packing models of [Ti₆Co₁₂] ring based on the titanium-capped cobalt clathrochelates[J]. Chin. Chem. Lett., 2021, 32(2): 923-925 doi: 10.1016/j.cclet.2020.04.004
12. [12]
  LIU X X, WANG Z R, CHEN G H, LI Q H, TAO J, ZHANG L. Cu₄Ti₄-oxo clusters functionalized by in situ-generated 2, 2′-biphenolate ligands from the oxidative coupling of phenols[J]. Dalton Trans., 2023, 52(7): 1857-1860 doi: 10.1039/D2DT03756D
13. [13]
  LIU Y J, FANG W H, ZHANG L, ZHANG J. Recent advances in heterometallic polyoxotitanium clusters[J]. Coord. Chem. Rev., 2020, 404: 213099 doi: 10.1016/j.ccr.2019.213099
14. [14]
  WANG C, LU Y J, RAO M Y, CHEN N, WANG S J, KONG F G. Co-crystal of Ti₄Ni₂ and Ti₈Ni₄ clusters with enhanced photochemical properties[J]. CrystEngComm., 2021, 23(24): 4402-4407 doi: 10.1039/D1CE00369K
15. [15]
  YU Y Z, GUO Y, ZHANG Y R, LIU M M, FENG Y R, GENG C H, ZHANG X M. A series of silver doped butterfly-like Ti₈Ag₂ clusters with two Ag ions panelled on a Ti₈ surface[J]. Dalton Trans., 2019, 48(35): 13423-13429 doi: 10.1039/C9DT02508A
16. [16]
  WANG D X, SAID A, LIU Y S, NIU H H, LIU C Y, WANG G, LI Z Y, TUNG C H, WANG Y F. Cr-Ti mixed oxide molecular cages: Synthesis, structure, photoresponse, and photocatalytic properties[J]. Inorg. Chem., 2022, 61(37): 14887-14898 doi: 10.1021/acs.inorgchem.2c02605
17. [17]
  YU Y Y, 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
18. [18]
  YU Y Y, 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
19. [19]
  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(23): 8685-8693 doi: 10.1021/acs.inorgchem.2c00327
20. [20]
  FANG W H, ZHANG L, ZHANG J. Synthetic strategies, diverse structures and tuneable properties of polyoxo-titanium clusters[J]. Chem. Soc. Rev., 2018, 47(2): 404-421 doi: 10.1039/C7CS00511C
21. [21]
  WANG C, LIU C, LI L J, SUN Z M. Synthesis, crystal structures, and photochemical properties of a family of heterometallic titanium oxo clusters[J]. Inorg. Chem., 2019, 58(9): 6312-6319 doi: 10.1021/acs.inorgchem.9b00508
22. [22]
  MANSOOR M A, MAZHAR M, MCKEE V, ARIFIN Z. Mn₂O₃-4TiO₂ semiconducting composite thin films for photo-electrochemical water splitting[J]. Polyhedron, 2014, 75: 135-140 doi: 10.1016/j.poly.2014.03.018
23. [23]
  YANG S, SU H C, HOU J L, LUO W, ZOU D H, ZHU Q Y, DAI J. The effects of transition-metal doping and chromophore anchoring on the photocurrent response of titanium-oxo-clusters[J]. Dalton Trans., 2017, 46(29): 9639-9645 doi: 10.1039/C7DT01603D
24. [24]
  LI N, MATTHEWS P D, LEUNG J J, KING T C, WOOD P T, LUO H K, WRIGHT D S. Synthesis, structure and properties of the manganese-doped polyoxotitanate cage [Ti₁₈MnO₃₀(OEt)₂₀(MnPhen)₃] (Phen=1, 10-phenanthroline)[J]. Dalton Trans., 2015, 44(44): 19090-19096 doi: 10.1039/C5DT03617H
25. [25]
  CHEN Y, JARZEMBSKA K N, TRZOP E, ZHANG L, COPPENS P. How does substitutional doping affect visible light absorption in a series of homodisperse Ti₁₁ polyoxotitanate nanoparticles?[J]. Chem. Eur. J., 2015, 21(32): 11538-11544 doi: 10.1002/chem.201500961
26. [26]
  CHEN Y, SOKOLOW J D, TRZOP E, COPPENS P. A manganese-doped polymeric framework of polyoxotitanate nanoclusters with a narrow band gap[J]. Dalton Trans., 2013, 42(43): 15285-15287 doi: 10.1039/c3dt52218k
27. [27]
  LV Y, CHENG J, MATTHEWS P D, HOLGADO J P, WILLKOMM J, LESKES M, STEINER A, FENSKE D, KING T C, WOOD P T, GAN L, LAMBERT R M, WRIGHT D S. A study of the optical properties of metal-doped polyoxotitanium cages and the relationship to metal-doped titania[J]. Dalton Trans., 2014, 43(23): 8679-8689 doi: 10.1039/c4dt00555d
28. [28]
  WU X, LI Q H, ZUO S E, LI Y, YI X D, YUAN L B, ZHENG L R, ZHANG J, DONG J C, WANG S B, ZHANG H B, ZHANG J. Bioinspired polyoxo-titanium cluster for greatly enhanced solar-driven CO₂ reduction[J]. Nano Lett., 2023, 23(24): 11562-11568 doi: 10.1021/acs.nanolett.3c03304
29. [29]
  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
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: e202424805 doi: 10.1002/anie.202424805
31. [31]
  TAUC J. Absorption edge and internal electric fields in amorphous semiconductors[J]. Mater. Res. Bull., 1970, 5: 721-729 doi: 10.1016/0025-5408(70)90112-1
1. [1]
  Pu ZHANG , Youzhu YU , Yuhua GUO , Zhongyuan ZHOU . Syntheses and photocatalytic CO₂ reduction properties of heterometallic Ni/Sn and Co/Sn oxo clusters. Chinese Journal of Inorganic Chemistry, 2026, 42(5): 1039-1047. doi: 10.11862/CJIC.20250353
2. [2]
  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
3. [3]
  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
4. [4]
  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
5. [5]
  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
6. [6]
  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
7. [7]
  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
8. [8]
  Yingjin Li , Jiaming Li , Hongjun Dong , Wenli Zhang , Liqiu Zhang , Xiulian Yin , Yun Wang , Zuoyi Liu , Chunmei Li . Recent research progress on metal-organic frameworks and their derivatives heterostructure for photocatalytic CO₂ reduction. Chinese Chemical Letters, 2026, 37(6): 112101-. doi: 10.1016/j.cclet.2025.112101
9. [9]
  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
10. [10]
  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
11. [11]
  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
12. [12]
  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
13. [13]
  Chunxuan Chen , Wanyuan Li , Chengyu Ni , Wubin Dai . Manganese valence modulation in ZnGa2O4 via simultaneously localized charge accumulation and oxygen vacancy engineering controlled by Li+ and F- substitutions for tailored applications. Chinese Journal of Structural Chemistry, 2026, 45(5): 100868-100868. doi: 10.1016/j.cjsc.2026.100868
14. [14]
  Rui Hu , Yidan Qi , Xingyu Wang , Yunhui Yang , Congyang Wang . Titanium-promoted conversion of N₂ into N-methylimides. Chinese Chemical Letters, 2026, 37(1): 111197-. doi: 10.1016/j.cclet.2025.111197
15. [15]
  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
16. [16]
  Juhong Lian , Deng Li , Yongmei Ma , Hui Bian , Yifan Shao , Zitong Wang , Junqing Yan , Ruibin Jiang , Shengzhong (Frank) Liu , Fuxiang Zhang . Decorating CsPbBr₃ with In₂O₃ seeds to build intimate direct Z-scheme heterojunction for promoted photocatalytic CO₂ reduction. Chinese Chemical Letters, 2025, 36(11): 111394-. doi: 10.1016/j.cclet.2025.111394
17. [17]
  Tianyi Zhou , Heng Yang , Guangbin Zhou , Feng Chen , Pan Gao . Recent advances of heterogeneous manganese catalysis in organic synthesis. Chinese Chemical Letters, 2026, 37(6): 112223-. doi: 10.1016/j.cclet.2025.112223
18. [18]
  Zhou Li , Mengxue Yu , Shixin Chang , Zhibin Huang , Zhenmin Cheng , Weibin Zhang , Sónia A. C. Carabineiro , Zhigao Xu , Kangle Lv . Enhancing the photocatalytic activity of crystalline g-C3N4 towards NO oxidation and CO2 reduction through K+-doping and cyano defect engineering. Chinese Journal of Structural Chemistry, 2026, 45(1): 100698-100698. doi: 10.1016/j.cjsc.2025.100698
19. [19]
  Hong Dong , Feng-Ming Zhang . Covalent organic frameworks for artificial photosynthetic diluted CO2 reduction. Chinese Journal of Structural Chemistry, 2024, 43(7): 100307-100307. doi: 10.1016/j.cjsc.2024.100307
20. [20]
  Ping Wang , Tianbao Zhang , Zhenxing Li . Reconstruction mechanism of Cu surface in CO2 reduction process. Chinese Journal of Structural Chemistry, 2024, 43(8): 100328-100328. doi: 10.1016/j.cjsc.2024.100328

Get Citation

PDF

XML

Metrics

PDF Downloads(0)
Abstract views(7)
HTML views(0)

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

Synthesis and photocatalytic CO2 reduction properties of heterometallic salicylate Mn/Ti clusters

Metrics

通讯作者: 陈斌, bchen63@163.com

Synthesis and photocatalytic CO₂ reduction properties of heterometallic salicylate Mn/Ti clusters