INTERNATIONAL JOURNAL OF HYDROGEN ENERGY
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2017
·
IF 3.582
Zongxiong Xu,Hao Fu,Tian Wen,Lei Zhang,Jian Zhang
Titanium-oxo clusters (TOCs) are important model complexes and potential precise single-source precursors of TiO 2 materials. We report here a series of TiO 2 samples derived from TOCs with the same wheel-like Ti 8 O 8 clustercore but different stabilizing ligands. Our results demonstrate that the ligands on TOCs not only influence the phase-transition during themolysis, but more importantly tune the photocatalytic H 2 evolution activities of the obtained TiO 2 materials. Through 500 °C calcination , the nanosized Ti 8 O 8 cluster stabilized by organic benzoate ligands gives rise to a TiO 2 sample with H 2 production rate of 611 μ mol/h/g. When the stabilizing ligands are changed to inorganic SO 4 2− , a significant improvement of H 2 evolution activity has been achieved, resulting in a 7-times higher value of 4527 μ mol/h/g. This work provides a new strategy to produce TiO 2 with enhanced and tunable photocatalytic activities from titanium-oxo cluster precursors.
研究领域:
材料科学
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化学
✓ 已验证
产品关联
DOI
高影响因子
INORGANIC CHEMISTRY
·
2022
·
IF 5.436
Xiao-Xue Liu,Guang-Hui Chen,Jun Tao,Jian Zhang,Lei Zhang
Exploring new structural types of polyoxotitanium clusters (PTCs), especially those containing classical polyoxometalates structures, has always been the focus of research in the field of metal-oxo clusters. In this work, we present the synthesis and characterization of three prismatic PTCs: namely, Ti8(μ2-O)3(μ4-O)2(OnPr)6(HOnPr)2(L1)8 (PTC-237; H2L1 = 3,5-di-tert-butylcatechol), Ti12(μ2-O)6(μ3-O)8(OnPr)6(L2)12(L3)2 (PTC-238; HL2 = 1-adamantanecarboxylic acid, HL3 = 2-picolinic acid), and [Ti18(μ2-O)4(μ3-O)16(μ5-O)2(OiPr)18(L3)8](L3)2 (PTC-239). Single-crystal X-ray diffraction analyses indicate that the construction of these prismatic PTCs is based on a stepwise interlayer assembly of {Ti3} and {Ti4} substructures. The diameters of their core skeletons are in the range between 0.9 and 1.3 nm. In particular, lacunary Linqvist-like {Ti4} and {Ti5} building units are found to exist in the structures of PTC-237 and PTC-239. According to the solid-state UV–vis diffuse reflectance measurements, the absorption band of 3,5-di-tert-butylcatecholate-functionalized PTC-237 shifts toward the visible-light region, giving a smaller optical band gap of 1.56 eV in comparison to PTC-238 (3.36 eV) and PTC-239 (3.25 eV).
研究领域:
材料化学
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无机化学
✓ 已验证
DOI
PubMed
高影响因子
INORGANIC CHEMISTRY
·
2021
·
IF 5.165
Amir Said,Chang Gao,Caiyun Liu,Huihui Niu,Dexin Wang,Yanshu Liu,Lin Du,Chen-Ho Tung,Yifeng Wang
A three-dimensional (3D) mesoporous material with an atomically precise structure, Ti16Pb5O16(C6H5CO2)2(OCH3)40 (Ti16Pb5), comprised of a novel high-nuclearity Pb-doped titanium oxide cluster (TOC), was synthesized. Ti16Pb5 exhibited a surface area of 45 m2 g–1 and a pore diameter of 3.5 nm. It exhibited an uptake capacity of I2 of ≤2.2 g g–1 in vapor, and the performance was maintained after seven uptake–release cycles. Ti16Pb5 also showed a high adsorption ratio and capacity (93% and 3.1 g g–1) in hexane. The characterization data, including Fourier transform infrared, Raman, and powder X-ray diffraction, suggested the lattice structure of Ti16Pb5 was rigid and I2 was accommodated in the pores of Ti16Pb5. To the best of our knowledge, this is the first example of using a TOC in I2 adsorption. In addition, Ti16Pb5 showed excellent activity and recyclability in visible-light degradation of dye pollutants and photocurrent generation. Our structural analysis suggested the alkoxide ligands within the channels of Ti16Pb5 build up a confined polar environment and thereby facilitate I2 accommodation, and meanwhile, the improved performances and stabilities of Ti16Pb5 are correlated with its cluster-based, 3D hierarchical structure.
研究领域:
材料科学
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环境科学
✓ 已验证
产品关联
DOI
PubMed
高影响因子
DALTON TRANSACTIONS
·
2023
·Vol. 52
·期 8
·2392-2403
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IF 4
Amir Said,Guanyun Zhang,Caiyun Liu,Dexin Wang,Huihui Niu,Yanshu Liu,Guanjie Chen,Chen-Ho Tung,Yifeng Wang
The cycloaddition reaction of CO2 to epoxides is quite promising for CO2 capture and storage as well as the production of value-added fine chemicals. Herein, a novel atomically precise lead-doped titanium-oxide cluster with the formula Ti10Pb2O16(phen)4(Ac)12(DMF)2 (denoted as Ti10Pb2; phen = 1,10-phenanthroline; Ac = acetate; DMF = dimethylformamide) was synthesized through a facile solvothermal process, and is a molecular photocatalyst with surface-anchored main-group metal active sites. Its structure was characterized by single-crystal X-ray diffraction and other complementary techniques. Ti10Pb2 showed high photo-response and charge-separation efficiency under simulated sunlight irradiation. Ti10Pb2 was successfully used in the cycloaddition reaction of CO2 with epoxides under solvent-free conditions. While its catalytic activity due to the Lewis acidity was moderate, simulated solar light irradiation further enhanced the reaction rate, demonstrating the synergistic effect of photocatalysis and Lewis-acid thermocatalysis.
研究领域:
化学
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材料科学
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环境科学
✓ 已验证
产品关联
DOI
PubMed
高影响因子
DALTON TRANSACTIONS
·
2020
·Vol. 49
·期 31
·11005-11009
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IF 4.174
Simin Hou,Qiaohong Li,Qing-Rong Ding,Yao Kang,Jian Zhang,Lei Zhang
Two heterometal-oxo Ag2Ti10 (PTC-221) and Ag4Ti8 (PTC-222) clusters were successfully synthesized and characterized, with the doped Ag atoms surrounded by the Ti–O core and exposed to the cluster surface, respectively. Density functional theory (DFT) calculations were carried out to study the electronic structures of PTC-221 and PTC-222, including the frontier orbitals and partial density of states (PDOS). The solid-state UV-vis absorption spectra of PTC-221 and PTC-222 were also recorded. Interestingly, PTC-221 shows intense visible light absorption with an absorption edge around 590 nm and exhibits good photocurrent response in the visible region.
研究领域:
无机化学
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材料科学
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计算化学
✓ 已验证
产品关联
DOI
PubMed
高影响因子
DALTON TRANSACTIONS
·
2017
·Vol. 46
·期 32
·10630-10634
·
IF 4.029
Mei-Yan Gao,Shumei Chen,Lan-Xia Hu,Lei Zhang,Jian Zhang
Four titanium-oxo-clusters with cyclohex-3-ene-1-carboxylate (Cec) ligands, Ti6(μ2-O)2(μ3-O)2(Cec)4(OiPr)12 (PTC-91; HOiPr = isopropanol), Ti6(μ3-O)6(Cec)6(OiPr)6 (PTC-92 and PTC-93) and H2[Ti18(μ2-O)11(μ3-O)14(Cec)20(OiPr)4] (PTC-94), have been solvothermally synthesized under different conditions, respectively. These clusters with the same Cec ligand show totally different structures, and they are stable in water and other common solvents. The Ti6 clusters with different conformations are presented in PTC-91, PTC-92 and PTC-93, while PTC-94 is an unusual Ti18 cluster. The photocatalytic studies reveal that PTC-91 and PTC-94 have good H2 evolution ability.
研究领域:
材料化学
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光催化
✓ 已验证
DOI
高影响因子
DALTON TRANSACTIONS
·
2017
·Vol. 46
·期 29
·9639-9645
·
IF 4.029
Shen Yang,Hu-Chao Su,Jin-Le Hou,Wen Luo,Dan-Hong Zou,Qin-Yu Zhu,Jie Dai
Titanium-oxo-clusters (TOCs), [Ti6O4(OiPr)10(Cat)2(BA)2] (1) and [Ti12M2O10(OEt)22(Cat)2(BA)4] (M = Co, Mn, Ni, 2–4; H2Cat = catechol, HBA = benzoic acid) are prepared in one step in an in situ solvothermal synthesis. Cluster structures of 2–4 can be considered as two 1 moieties merged together by two transition metal atoms. Unlike most TOCs with sphere-like structures, clusters 2–4 feature a unique single layered structure. They are not only transition metal doped TOCs but also charge transfer (CT) TOCs, CT from Cat to the TiO cluster core. Photoelectrodes were prepared by dipping the solution of clusters on a porous TiO2 substrate. Photocurrent response properties of the electrodes were studied in comparison with those of the electrodes of non-metal doped 1 and the non-Cat coordinated Ti6 cluster. The results showed that the photocurrent densities of metal doped clusters are higher than that of non-doped clusters and the highest photocurrent density was found for the redox active Co(II) doped cluster. Charge transfer also plays an effective role in photocurrent conversion under visible light irradiation.
研究领域:
材料科学
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光电化学
✓ 已验证
DOI
高影响因子
CHEMISTRY-A EUROPEAN JOURNAL
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2020
·Vol. 26
·期 30
·6894-6898
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IF 4.857
Shuyu Zhou,Congping Li,Hao Fu,Jing Cao,Jian Zhang,Lei Zhang
Graphical Outstanding resemblance ! The first molecular model of perovskite PbTiO 3 has been successfully prepared by bottom-up assembly of lead-doped titanium-oxo clusters in the presence of p - tert -butylthiacalix[4]arene as stabilizing ligands. Structural characterization confirmed that the clusters have almost the same structure as that in PbTiO 3 (see figure). The nanoclusters showed high solution stability and can be applied as electron-transport materials in perovskite solar cells to give satisfactory efficiencies and high device stability. In this work we have successfully prepared two lead-doped titanium-oxo clusters with core structures that resemble isolated perovskite PbTiO 3 species. In the obtained highly symmetric Pb 8 Ti 7 -oxo cluster, the central TiO 6 octahedra are orthogonally extended to adjacent octahedra through corner-sharing and the eight dopant lead ions form a cubic arrangement, making it the first molecular model of perovskite PbTiO 3 . Moreover, the clusters readily dissolved in chloroform and showed high solution stability, as confirmed by MALDI-TOF MS measurements. Based on such solution processability, they can be easily spin-coated to form homogeneous films, which were employed as electron-transport materials in perovskite solar cells to give an average power conversion efficiency of around 15 % and improved device stability. This newly developed bottom-up cluster assembly method provides an efficient approach to the construction of atomically precise models of perovskite metal oxides as well as potential molecular tools to extend their applications.
研究领域:
材料化学
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能源科学
✓ 已验证
产品关联
DOI
PubMed
高影响因子
INORGANIC CHEMISTRY
·
2021
·
IF 5.165
Chao Wang,Shou-Juan Wang,Fan-Gong Kong
Three photosensitive tert-butylcalix[n]arene (TBC[n], n = 4, 6, 8)-protected titanium-oxo clusters (TOCs), formulated as [Ti4(μ3-O)2(TBC[4])2(OiPr)4(DEF)2]·DEF (1, TBC[4]-Ti4, DEF = N,N-diethylformamide), [Ti4(μ4-O)TBC[6](OCH3)9]·H2O (2, TBC[6]-Ti4), and [Ti4(μ3-O)2(OiPr)4TBC[8](DEF)2]·DEF (3, TBC[8]-Ti4), were successfully synthesized and characterized. Because of the generation of charge transfer from TBC[n] to the TiO core, the three TBC[n]-decorated TOCs show a broadened visible-light absorption and narrowed optical band gap based on the UV–visible spectra and density functional theory calculations. The corresponding photosensitive electrodes prepared using these three TOCs exhibit stable photocurrent responses. Furthermore, their photocatalytic performances for hydrogen evolution and methylene blue degradation were evaluated, and all of the materials display excellent photocatalytic activity and stability. The calixarene-Ti coordination is therefore an effective strategy to enlarge the visible-light absorption band of Ti–O materials and improve their photoelectric/photocatalytic performances.
研究领域:
材料化学
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光催化
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理论计算
✓ 已验证
产品关联
DOI
PubMed
高影响因子
Inorganic Chemistry Frontiers
·
2022
·Vol. 9
·期 5
·959-967
·
IF 7.779
Chao Wang,Shoujuan Wang,Fangong Kong,Ning Chen
Sensitized Ti-oxo clusters have attracted growing attention as analogous molecular model compounds of dye-sensitized titanium dioxide solar cells. However, reports on the introduction of metal complexes as photosensitizers into Ti-oxo clusters are still very rare. Herein, with the use of an organometallic complex ferrocene as a sensitizer, two novel ferrocene-sensitized Ti-oxo clusters, namely, [Ti8(μ3-O)4(Dipa)2(Fcdc)4(OiPr)10]·2HOiPr (H2Fcdc = 1,1-ferrocene dicarboxylic acid, Dipa = diisopropanolamine, and HOiPr = isopropanol, Ti8Fcdc4) and [Ti10(μ4-O)2(μ3-O)4(Fcdc)2(μ2-OEt)8(OEt)10]·2HOEt (Ti10Fcdc2) have been successfully synthesized. Their molecular structures, light absorption, charge transfer, and photoelectrochemical properties were systematically investigated. It is demonstrated that the incorporation of Fcdc ligands shows a significant influence on the light absorption of the resulting clusters, and their absorption band edge is extended to about 580 nm. Furthermore, experimental measurements and theoretical calculations showed that the intense intramolecular charge transfer occurs from the Fcdc ligands to the Ti-oxo core. Based on these advantages, clusters Ti8Fcdc4 and Ti10Fcdc2 were used as photoelectrode precursors to carry out photoelectrochemical experiments, and both exhibited clear photocurrent responses. The molecular structure, light absorption, and effective charge transfer of materials have a direct bearing on their photoelectrochemical performances. This work not only provides novel structural models for sensitized Ti-oxo clusters towards the modulation of photoelectric properties but also provides new insights into further understanding the structure–property relationships of sensitized clusters.
研究领域:
材料科学
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化学
✓ 已验证
DOI
高影响因子
DALTON TRANSACTIONS
·
2020
·Vol. 49
·期 18
·5957-5964
·
IF 4.174
Weiming Liu,Caiyun Liu,Wenli Wu,Guanyun Zhang,Jian Zhang,Chen-Ho Tung,Yifeng Wang
For the preparation of aqueous Ti-oxo clusters (TOCs) without organic ligands, organic ammonium cations (OACs) are important, but the mechanism is obscure. Here, the Ti4+/SO42− system was chosen as a model to investigate the roles of OACs. Three {Ti4} clusters were isolated from this system with different cationic additives. Structural analysis revealed a structural role of OACs: the hierarchically ordered array of the OACs in the organic layers was responsible for the stability and formation of crystalline precipitates. 17O NMR spectroscopy was used to study the interactions of OACs and SO42− with the Ti-oxo species in water under highly acidic conditions. SO42− enhanced the condensation of Ti4+ by binding to the TOC species. OACs could not enhance the condensation of Ti4+ but could change the solution speciation and especially promote the formation of {Ti18O27} clusters. We speculate that OACs interact with the cationic/neutral TOCs through anionic bridges to change the speciation. Under the synthetic conditions of {Ti4}, {Ti18O27} is the native TOC in solutions but {Ti4} is not.
研究领域:
无机化学
·
材料科学
·
分析化学
✓ 已验证
DOI
高影响因子
INORGANIC CHEMISTRY
·
2022
·
IF 5.436
Yue Mao,Guang-Hui Chen,Xiaofeng Yi,Yao Kang,Jian Zhang,Lei Zhang
In this study, with the assistance of quaternary ammonium salts we have successfully prepared a new family of salicylate-stabilized heterobimetallic Pb–Ti–oxo clusters, including H(TEA)[Pb2Ti6(μ2-O)2(μ3-O)2(OiPr)4(PA)2(Sal)6(NO3)2] (PTC-321; TEA = tetraethylammonium; HOiPr = isopropanol; H2PA = phenylphosphonic acid; H2Sal = salicylic acid), {PbTi3(μ2-O)(μ3-O)(OiPr)2(PA)(Sal)3(DMF)·CH3CN}n (PTC-322; DMF = dimethylformamide), {PbTi5(μ3-O)6(Sal)3(CH3COO)2(DMF)(OiPr)2}n (PTC-323), [Pb2Ti4(Sal)6(EtO)2(OiPr)6(HOiPr)2]·CH3NH2 (PTC-324; EtOH = CH3CH2OH), H[Pb4Ti9(μ2-O)2(μ3-O)(μ4-O)6(Sal)7(OiPr)13] (PTC-325), and Pb2Ti12(μ2-O)3(μ3-O)3(μ4-O)4(Sal)4(OEt)24 (PTC-326). Single-crystal X-ray diffraction studies demonstrate that the {Ti3Pb(Sal)3} unit acts as the building block to constitute the diverse assembly of PTC-321–PTC-323. Thereinto, the clusters in PTC-322 and PTC-323 are connected into infinite one-dimensional chains. Furthermore, the solvent effects have facilitated the heterobimetallic Pb–Ti–oxo clusters into various configurations in PTC-323–PTC-326. Solid-state ultraviolet–visible spectroscopy analysis indicates that the optical absorption bands of these compounds shift effectively toward the visible-light region, and they were also employed as electrode precursors to investigate their visible-light-driven photocurrent response.
研究领域:
无机化学
·
材料科学
✓ 已验证
产品关联
DOI
PubMed
高影响因子
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