Syntheses and photocatalytic CO2 reduction properties of heterometallic Ni/Sn and Co/Sn oxo clusters
【无机化学学报】doi: 10.11862/CJIC.20250353
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.
【无机化学学报】doi: 10.11862/CJIC.20240255
采用原位聚合法制备了氯氧化铋(BiOCl)与聚苯胺(PANI)复合的Ⅱ型异质结光催化剂BiOCl/PANI,并采用X射线衍射(XRD)、傅里叶变换红外光谱(FTIR)、透射电子显微镜(TEM)、X射线光电子能谱(XPS)、紫外可见漫反射光谱(UV-Vis DRS)和N2吸附-脱附测试等多种技术手段对其进行了表征,考察了BiOCl/PANI在模拟可见光下对罗丹明B (RhB)的光催化降解性能。实验结果表明:BiOCl/PANI催化剂比PANI和BiOCl具有更高的光催化活性,在RhB质量浓度为50 mg·L-1、PANI与BiOCl的物质的量之比为0.02∶1、50 mg·L-1的催化剂条件下,所制备的BiOCl/PANI光催化150 min后,RhB降解率为98.8%,速率常数为0.031 min-1;经过4次循环实验后,RhB降解率从98.8%降低至98.4%,表现出良好的稳定性和可重复利用性。光催化剂BiOCl/PANI实现了电子和空穴对的快速分离,降低了二者在催化剂内部的复合速率,提高了光催化性能。
【大学化学】doi: 10.12461/PKU.DXHX202405147
仪器分析实验“分子荧光法测定罗丹明B的含量”存在实验过于简单、未考虑实际情况等问题。因此,本改进实验在三维荧光扫描模式下获取样本数据,不进行复杂预处理,而是运用化学计量学算法解析出目标分析物的纯信号,进而实现了染色辣椒中罗丹明6G和123的同时测定。本改进实验提高了学生全面考虑问题和创新解决问题的能力。
【无机化学学报】doi: 10.11862/CJIC.20230433
Graphitic carbon nitride (CN)-based materials were synthesized using melamine, urea, guanidine carbonate, and thiourea as precursors via pyrolysis. The synthesized materials underwent comprehensive characterization employing techniques such as X-ray diffraction (XRD), scanning electron microscopy (SEM), X-ray photoelectron spectroscopy (XPS), and nitrogen adsorption-desorption test. These materials were evaluated for their performance as cathodes with platinum sheet electrodes as anodes in the selective electrocatalytic reduction of Sn(Ⅳ) in an acid solution. During the reduction of Sn(Ⅳ) to Sn(Ⅱ), Sn(Ⅱ) can also be reduced to Sn due to the similar reduction potentials of Sn(Ⅱ) and Sn(Ⅳ). The deposition of Sn on the cathode diminishes the electrode conductivity efficiency. Therefore, the electrode material must fulfill the dual requirements of reducing Sn(Ⅳ) to Sn(Ⅱ) while preventing the reduction of Sn(Ⅱ) to Sn. In comparison to conventional cathode materials such as copper plates, graphite plates, ruthenium iridium titanium plates, and platinum plates, the CN demonstrated superior performance in the selective electrocatalytic reduction of Sn(Ⅳ) in an acidic solution. In addition, CN exhibited a lower potential in a dual-electrode electrolytic cell and maintained stability under acidic conditions, enabling the selective reduction of Sn(Ⅳ) to Sn(Ⅱ).
【无机化学学报】doi: 10.11862/CJIC.20240003
合成了2个丁二酮肟有机锡化合物:双(三(2-甲基-2-苯基丙基)锡)丁二酮肟配合物(C6H5C(CH3)2CH2)3Sn(ON=C(CH3)C(CH3)=NO)Sn(CH2C(CH3)2C6H5)3 (1)和二苄基锡氧氯丁二酮肟多核配合物[μ3-O-((C6H5CH2)2Sn)2(ON=C(CH3)C(CH3)=NOH)(O)Cl]2(2)。通过元素分析、红外光谱、核磁共振(1H、13C、119Sn)、差热分析和单晶X射线衍射对配合物进行了结构表征,对其结构进行量子化学从头计算,并进行了体外抗癌活性研究。结果显示:配合物1为通过配体丁二酮肟桥联的双锡核中心对称分子,锡原子均为四配位的畸变四面体构型;配合物2为通过氧原子和丁二酮肟配体桥联的四锡核中心对称多环聚合结构,锡原子分别为五配位的畸变三角双锥构型和六配位的畸变八面体构型。配合物对人肝癌细胞(HUH7)、人肺癌细胞(A549)、人表皮癌细胞(A431)、人结肠癌细胞(HCT-116)和人乳腺癌细胞(MDA-MB-231)均有较强的抑制活性。
Synthesis, structure, and properties of hydrated tricyclohexyltin theophylline-7-acetic acid complex
【无机化学学报】doi: 10.11862/CJIC.20250244
The hydrated tricyclohexyltin theophylline-7-acetic acid (tpH) complex [Sn(C6H11)3(tp)(H2O)] was synthesized via an ethanol solvothermal method using tricyclohexyltin hydroxide and tpH in a 1∶1 molar ratio. The complex was characterized by IR, 1H (13C) NMR, elemental analysis, and powder X-ray diffraction, and the crystal structure was determined by single-crystal X-ray diffraction. The crystal belongs to the orthorhombic system with space group Iba2, and the central tin atom is in a five-coordinated trigonal bipyramidal configuration. Quantum chemistry ab initio calculations were performed to investigate the stability, molecular orbital energy, and frontier molecular orbital characteristics of the complex. Additionally, its thermal stability, electrochemical properties, and in vitro anticancer activity were evaluated.
【无机化学学报】doi: 10.11862/CJIC.20240219
A simple two-step hydrothermal method synthesized four different CdS/Fe3O4 photocatalysts with varying ratios of mass of CdS to Fe3O4. The composition and morphology of the prepared samples were investigated using X-ray diffraction (XRD), Raman spectrum, X-ray photoelectron spectroscopy (XPS), scanning electron microscopy (SEM), and transmission electron microscopy (TEM). Solid UV reflectance spectra testing found that CdS/Fe3O4 nanocomposites had good light absorption throughout the spectral range, promoting their photocatalytic properties. Under visible light irradiation, CdS/Fe3O4 (2:5) with a mass ratio of 2:5 exhibited excellent photocatalytic performance, with a degradation rate of 98.8% for rhodamine B. Furthermore, after five cycles of photocatalytic degradation reaction, the rhodamine B degradation rate remained at 96.2%, indicating that the photocatalysts have good photocatalytic stability.
【无机化学学报】doi: 10.11862/CJIC.20250028
A flower-like BiOBr photocatalyst (CS/BiOBr) was prepared by using the carbon material derived from corn straw (CS) as the carrier. The prepared composites were characterized by X - ray diffraction (XRD), Fourier transform infrared (FIIR) spectra, scanning electron microscope (SEM), X - ray photoelectron spectra (XPS), and UV-Vis diffuse reflectance spectra (UV-Vis DRS). The SEM analyses indicate that the introduction of CS promotes the formation of a unique flower-like structure in BiOBr, which not only optimizes the efficiency of light capture but also increases the specific surface area of BiOBr. The bandgap of the composite was narrower compared with the pure BiOBr. The CS/BiOBr composites exhibited higher photocatalytic activity than pure CS and BiOBr under visible light irradiation, and a higher first-order reaction rate constant (k) of 0.043 7 min-1 than BiOBr (0.014 6 min-1), and exhibited excellent stability and reusability during the cyclic run. The enhanced photocatalytic activity is attributed to the efficient separation of photoinduced electrons and holes. Superoxide radicals and holes were the major active species.
【物理化学学报】doi: 10.3866/PKU.WHXB202402006
有机-无机卤化物钙钛矿太阳能电池(PSCs)因其优异的光伏性能(PCE)和简单的制备工艺而受到广泛关注。然而,界面处的电荷复合是制约PSCs光电转换效率进一步提高的关键因素。本文基于旋涂镀膜法利用室温合成的六氯锡酸铵(AH)晶体对钙钛矿薄膜(PSK)和电子传输层之间的界面进行修饰。AH是一种无机锡基钙钛矿材料,可以钝化PSK中的缺陷,建立更好的晶格匹配,从而提高PSK的质量和结晶度。开尔文探针力显微镜结果证实,AH促进了光生电子的定向迁移。飞秒瞬态吸收光谱结果说明AH有效缩短了电子抽取寿命,促进了界面电子转移。基于AH改性的优点,AH修饰的PSCs具有更高的PCE和更小的迟滞效应。
【无机化学学报】doi: 10.11862/CJIC.20250311
Bi2O3@BiVO4 composites were synthesized using the solvothermal method with ethylene glycol as the solvent. Bi2O3 was grown on the surface of BiVO4 by regulating the reaction temperature. The adsorption performance of the composite for rhodamine B (RhB) was investigated. The results indicate that the reaction temperature significantly impacts the morphology and adsorption performance of Bi2O3@BiVO4. The Bi2O3@BiVO4 composite prepared at 180 ℃ (180-BO@BVO) consisted of nanoparticles with an average size of 7 nm, featuring a higher concentration of oxygen vacancies on the surface, but with a lower specific surface area (only 1.2 m2·g-1). 180-BO@BVO, with oxygen species adsorbed at surface oxygen vacancies carrying a negative charge, achieved an impressive RhB removal efficiency of up to 83.0% through electrostatic interaction with RhB. The adsorption process follows the Langmuir isotherm and the pseudo-second-order kinetic model, suggesting that it is predominantly governed by chemical adsorption. After five cycles of adsorption experiments, the removal efficiency of RhB by composites remained basically unchanged (more than 80%), demonstrating excellent regeneration performance.
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