Synthesis and CO2 photocatalytic reduction of heterometallic one-dimensional titanium-based coordination polymers

IF 4 2区化学 Q2 CHEMISTRY, PHYSICAL

Journal of Molecular Structure Pub Date : 2025-06-13 DOI:10.1016/j.molstruc.2025.142978

Yuanyuan Zhang , Yaomei Fu , Xiaoyan Gu , Liang Zhao , Junning Kou , Chao Qin

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Abstract

Four new transition metal doped one-dimensional titanium-based coordination polymers, [Ti₂L₂M(phen)] (M = Co²⁺, Ni²⁺, Cu²⁺, Zn²⁺, L = Embonic acid, phen = 1,10-phenanthroline), have been synthesized under solvothermal conditions utilizing the Ti₄L₆ precursors. In the structure of [Ti₂L₂M(phen)], a dinuclear titanium cluster is formed by coordinating two Ti atoms with two L ligands. The oxygen atoms from the carboxylate groups of the L ligands, which possess vacant coordination sites, further interact with the M(phen) unit, resulting in a Z-shaped one-dimensional chain-like structure. All compounds are determined by single crystal X-ray diffraction analysis, thermogravimetric analysis, PXRD, UV–vis and IR spectra. Notably, all frameworks exhibit excellent stability and can be used as heterogeneous catalysts to reduce CO₂ to syngas (CO+H₂) under light conditions. Specifically, the total yield of syngas for Ti₂L₂Co is up to 20.3 mmol g^–1 h^–1

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异金属一维钛基配位聚合物的合成及CO2光催化还原

以Ti4L6为前驱体，在溶剂热条件下合成了四种新的过渡金属掺杂一维钛基配位聚合物[Ti2L2M(phen)] （M = Co2+, Ni2+, Cu2+, Zn2+, L = embononic acid, phen = 1,10-菲罗啉）。在[Ti2L2M(phen)]结构中，两个钛原子与两个L配体配位形成双核钛簇。L配体的羧酸基氧原子具有空位配位，进一步与M（phen）单元相互作用，形成z形的一维类链结构。所有化合物均通过单晶x射线衍射分析、热重分析、PXRD、UV-vis和IR光谱测定。值得注意的是，所有框架都表现出优异的稳定性，可以作为多相催化剂在光照条件下将CO2还原为合成气（CO+H2）。具体来说，Ti2L2Co的合成气总产率高达20.3 mmol g-1 h-1

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来源期刊

Journal of Molecular Structure 化学-物理化学

CiteScore

7.10

自引率

15.80%

发文量

2384

审稿时长

45 days

期刊介绍： The Journal of Molecular Structure is dedicated to the publication of full-length articles and review papers, providing important new structural information on all types of chemical species including: • Stable and unstable molecules in all types of environments (vapour, molecular beam, liquid, solution, liquid crystal, solid state, matrix-isolated, surface-absorbed etc.) • Chemical intermediates • Molecules in excited states • Biological molecules • Polymers. The methods used may include any combination of spectroscopic and non-spectroscopic techniques, for example: • Infrared spectroscopy (mid, far, near) • Raman spectroscopy and non-linear Raman methods (CARS, etc.) • Electronic absorption spectroscopy • Optical rotatory dispersion and circular dichroism • Fluorescence and phosphorescence techniques • Electron spectroscopies (PES, XPS), EXAFS, etc. • Microwave spectroscopy • Electron diffraction • NMR and ESR spectroscopies • Mössbauer spectroscopy • X-ray crystallography • Charge Density Analyses • Computational Studies (supplementing experimental methods) We encourage publications combining theoretical and experimental approaches. The structural insights gained by the studies should be correlated with the properties, activity and/ or reactivity of the molecule under investigation and the relevance of this molecule and its implications should be discussed.