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1.
沈荣晨  郝磊  陈晴  郑巧清  张鹏  李鑫 《物理化学学报》2022,38(7):2110014-41
随着化石燃料使用的增加和温室气体排放量持续上升,20世纪以来气温上升得更快。开发环境友好型能源取代传统化石燃料是当务之急。氢能源作为一种清洁、高效的能源,被认为是最有希望取代传统化石燃料的能源。光催化水分解水产氢作为为一种环保型技术被认为是最有前景的氢能生产方法。提高光生电子-空穴对分离效率是构建高效光催化剂的关键。然而,利用高度分散的助催化剂构建高效、稳定的产氢光催化剂仍然是一个挑战。本文首次成功地采用一步原位高温磷化法制备了高度分散的非贵金属三金属过度金属磷化Co0.2Ni1.6Fe0.2P助催化剂(PCNS-CoNiFeP)掺杂P的石墨相氮化碳纳米片(PCNS)。有趣的是,PCNS-CoNiFeP与传统氢氧前驱体磷化法制备的CoNiFeP相比,没有聚集性,分散性高。X射线衍射(XRD)、X射线光电子能谱(XPS)、元素映射图像和高分辨率透射电镜(HRTEM)结果表明,PCNS-CoNiFeP已成功合成。紫外-可见吸收光谱结果表明,PCNS-CoNiFeP在200–800 nm波长范围内较PCNS略有增加。光致发光光谱、电化学阻抗谱(EIS)和光电流分析结果表明,CoNiFeP助催化剂能有效促进光生电子-空穴对的分离,加速载流子的迁移。线性扫描伏安法(LSV)结果还表明,负载CoNiFeP助催化剂可大大降低CNS的过电位。结果表明,以三乙醇胺溶液为牺牲剂的PCNS-CoNiFeP最大产氢速率为1200 μmol·h-1·g-1,是纯CNS-Pt (320 μmol·h-1·g-1)的4倍。在420 nm处的表观量子效率为1.4%。PCNS-CoNiFeP在光催化反应中也表现出良好的稳定性。透射电镜结果表明,6–8 nm的CoNiFeP高度分散在PCNS表面。高度分散的CoNiFeP比聚集的CoNiFeP具有更好的电荷分离能力和更高的电催化析氢活性。由此可见,聚合的CoNiFeP-PCNs (300 μmol·h-1·g-1)的产氢速率远低于PCNS-CoNiFeP。此外,CNS的P掺杂可以改善其电导率和电荷传输。  相似文献   
2.
Photocatalytic CO2 reduction to C1 fuels is considered to be an important way for alleviating increasingly serious energy crisis and environmental pollution. Due to the environment-friendly, simple preparation, easy formation of highly-stable metal-nitrogen(M-Nx) coordination bonds, and suitable band structure, polymeric carbon nitride-based single-atom catalysts(C3N4-based SACs) are expected to become a potential for CO2 reduction under visible-light irradiation. In this review, we summarize the recent advancement on C3N4-based SACs for photocatalytic CO2 reduction to C1 products, including the reaction mechanism for photocatalytic CO2 reduction to C1 products, the structure and synthesis methods of C3N4-based SACs and their applications toward photocatalytic CO2 reduction reaction(CO2RR) for C1 production. The current challenges and future opportunities of C3N4-based SACs for photoreduction of CO2 are also discussed.  相似文献   
3.
通过硬模板法设计、制备了一种具有径向内排列骨架的内放射状中空TiN纳米颗粒(IRHTiNs),并将其与硫(S)复合制备锂硫电池(LSB)正极。随后采用扫描电子显微镜(SEM)、透射电子显微镜(TEM)、X射线光电子能谱(XPS)和热重分析(TGA)表征了IRHTiNs及IRHTiNs/S复合正极的结构及成分。在电化学测试中,与C正极相比,以IRHTiNs为正极的LSB表现出了1 250mAh·g-1的高初始比容量,LSB的容量衰减速度明显降低,电池性能显著提升。  相似文献   
4.
表面增强拉曼光谱技术对分子具有特异性识别以及快速无损检测的能力,使其在药物检测方面具有重大的潜力。通过贵金属和氮化钛之间协同作用,使复合基底具有较高的SERS性能,提供了一种基于SERS技术的药物检测方法。采用电化学沉积及自组装法,制备出贵金属/氮化钛复合薄膜。研究表明,在复合薄膜中存在面心立方晶型TiN、金属单质Au和Ag三种物相;电子显微镜显示平均粒径分别为90和50 nm的金属Au和Ag颗粒均匀分布在TiN薄膜表面;基底的紫外-可见吸收图谱中出现了贵金属金与银纳米颗粒及TiN薄膜三者的特征等离子体共振吸收峰。以该复合薄膜为SERS基底,对烟酸溶液进行拉曼检测。结果显示,贵金属/氮化钛复合薄膜对烟酸具有显著的SERS效应,最低检测浓度为10-5 mol·L-1,对1 033 cm-1处烟酸拉曼信号强度及浓度取对数,发现两者间呈一定线性关系,其R2为0.969,得益于TiN,Au和Ag之间可发生表面等离子体共振引起电磁场增强,以及电荷转移效应。研究还发现,烟酸通过COO-基团垂直吸附在贵金属/氮化钛基底表面;在酸性环境下,烟酸N原子质子化主要以阳离子N+H(Ⅰ)形式存在;在碱性环境时,主要以阴离子COO-(Ⅲ)形式存在。绞股蓝总甙溶液中模拟烟酸非法添加,该复合基底对其最低的拉曼检测浓度是10-5 mol·L-1,为现场快速检测非法添加药物提供了新途径。  相似文献   
5.
刘嘉成  吴超  夏功榆  郑骑林  朱志宏  徐平 《中国物理 B》2022,31(1):14201-014201
We designed a reconfigurable dual-interferometer coupled silicon nitride microring resonator.By tuning the integrated heater on interferometer's arms,the"critical coupling"bandwidth of resonant mode is continuously adjustable whose quality factor varies from 7.9×104 to 1.9×105 with the extinction ratio keeping higher than 25 dB.Also a variety of coupling spanning from"under-coupling"to"over-coupling"were achieved,showing the ability to tune the quality factor from 6.0×103 to 2.3×105.Our design can provide an adjustable filtering method on silicon nitride photonic chip and contribute to optimize the nonlinear process for quantum photonics and all-optical signal processing.  相似文献   
6.
Qiu-Ling Qiu 《中国物理 B》2022,31(4):47103-047103
The strong polarization effect of GaN-based materials is widely used in high-performance devices such as white-light-emitting diodes (white LEDs), high electron mobility transistors (HEMTs), and GaN polarization superjunctions. However, the current researches on the polarization mechanism of GaN-based materials are not sufficient. In this paper, we studied the influence of polarization on electric field and energy band characteristics of Ga-face GaN bulk materials by using a combination of theoretical analysis and semiconductor technology computer-aided design (TCAD) simulation. The self-screening effect in Ga-face bulk GaN under ideal and non-ideal conditions is studied respectively. We believe that the formation of high-density two-dimensional electron gas (2DEG) in GaN is the accumulation of screening charges. We also clarify the source and accumulation of the screening charges caused by the GaN self-screening effect in this paper and aim to guide the design and optimization of high-performance GaN-based devices.  相似文献   
7.
A novel solid-phase microextraction coating of phosphorous-containing titanium oxide composite was developed using titanium fiber as a support and a titanium source by hydrothermal oxidation in a phosphoric acid solution containing hydrogen peroxide. The morphology of the fiber coatings was controlled by the conditions of the hydrothermal oxidation reaction. The oriented nanofiber coating was employed to extract several types of representative aromatic analytes. The experimental results demonstrated that the as-prepared fiber exhibited excellent extraction efficiency toward polycyclic aromatic hydrocarbons. Combined with high-performance liquid chromatography with ultraviolet detection, main extraction conditions were optimized, including pH, ionic strength, extraction temperature, stirring rate, extraction time and desorption time. The established method presented good linearity from 0.05 to 200 μg/L with limit of detection ranging from 0.012 to 0.126 μg/L. This convenient and green procedure was suitable for the selective extraction and determination of typical polycyclic aromatic hydrocarbons in environmental water samples. The relative recoveries of 85.8–112% were obtained for the determination of target polycyclic aromatic hydrocarbons in water samples spiked with 5.0 and 15.0 μg/L. Moreover, the as-prepared fiber showed at least 210 extraction/desorption cycles due to its high mechanical and chemical stability.  相似文献   
8.
通过溶剂热合成方法,以吡啶-2-甲醛肟(HPycox)和Ti(OiPr)4合成了双核钛配合物[Ti2μ2-O)(Pycox)2(OiPr)4] (1)。通过结构分析,分别使用二苯基膦酸和苯基膦酸对其进行结构调控,成功制备了三核钛配合物[Ti3μ2-O)2(Pycox)2(Ph2PO22(OiPr)4] (2)和六核钛配合物[Ti6μ2-O)2μ3-O)2(Pycox)2(PhPO34(OiPr)6]·2CH3CN (3)。配合物1~3的光学带隙分别为2.89、3.00和2.87 eV,其中配合物2的光电流密度可达0.1 μA·cm-2。  相似文献   
9.
Studies on N2 activation and transformation by transition metal hydride complexes are of particular interest and importance. The synthesis and diverse transformations of a dinitrogen dititanium hydride complex bearing the rigid acridane-based acriPNP-pincer ligands {[(acriPNP)Ti]2(μ2-η1:η2-N2)(μ2-H)2} are presented. This complex enabled N2 cleavage and hydrogenation even without additional H2 or other reducing agents. Furthermore, diverse transformations of the N2 unit with a variety of organometallic compounds such as ZnMe2, MgMe2, AlMe3, B(C6F5)3, PinBH, and PhSiH3 have been well established at the rigid acriPNP-ligated dititanium framework, such as reversible bonding-mode change between the end-on and side-on/end-on fashions, diborylative N=N bond cleavage, the formal insertion of two dimethylaluminum species into the N=N bond, and the formal insertion of two silylene units into the N=N bond. This work has revealed many unprecedented aspects of dinitrogen reaction chemistry.  相似文献   
10.
Facile α‐H elimination from tetrakis(trimethylsilylmethyl)titanium precursors to give adducts of (alkylidene)bis(alkyl)titanium complexes is induced by light alkali metal amides of the NNNN‐type macrocyclic anionic ligand Me3TACD [(Me3TACD)H=1,4,7‐trimethyl‐1,4,7,10‐tetraazacyclododecane]. In the crystal, the alkali metal interacts with the carbene carbon atom or with the CH2 group of the trimethylsilymethyl ligand. The nucleophilic character of the carbene carbon atom was shown by the reaction with benzophenone and terminal acetylenes.  相似文献   
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