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941.
942.
943.
吡啶酰胺基配体与Mn~(2 )、Fe~(3 )、Ru~(3 )配合物的合成和催化环己烯的氧化反应 总被引:4,自引:0,他引:4
由于吡啶环较一般芳环更稳定,抗氧化能力强,且毗院环上氮的孤电子对与中心金属的d轨道通过配位作用可组成更大的共轭体系,增强了中心金属与配体之间电子云的流动性,从而可调节金属配合物与氧形成超氧、过氧或单氧活性物种的电子云分布(包括电荷分布),进而影响其催化活性和选择性U,’1。根据这一构想,本文合成了含毗院酚胺基配体的金属Mn,Fe,Ru的配合物,在纯氧作氧源下,考察了它们催化环己烯氧化反应的性能。1催化剂的制备称取20mmolZ一毗陡甲酸溶于sml毗院中,10mmoll,2一乙M胺(或1,个丁M胺… 相似文献
944.
不含金属的碳材料通过廉价且易获得的柚子皮经KOH活化和高温热解获得,该碳材料具有高比表面积(1 055 m~2·g~(-1))和高石墨化程度的类蜂窝状结构。将多孔碳(PAC)材料修饰后的电极作为工作电极,采用阳极溶出伏安法(SWASV)同步检测Cd~(2+)、Pb~(2+)和Cu~(2+)离子,表现出较高的灵敏度、可重复性、稳定性和较低的检测限。研究认为PAC的微孔和中孔可以充当有效的离子传递通道,从而加速离子的扩散并显著提高交换效率,而高的石墨化程度提高了材料的导电性,加速了电子传输。 相似文献
945.
Linli Zhang Yitian Tang Zhaobin Han Kuiling Ding 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2019,131(15):5027-5031
A series of MnI complexes containing lutidine‐based chiral pincer ligands with modular and tunable structures has been developed. The complex shows unprecedentedly high activities (up to 9800 TON; TON=turnover number), broad substrate scope (81 examples), good functional‐group tolerance, and excellent enantioselectivities (85–98 % ee) in the hydrogenation of various ketones. These aspects are rare in earth‐abundant metal catalyzed hydrogenations. The utility of the protocol have been demonstrated in the asymmetric synthesis of a variety of key intermediates for chiral drugs. Preliminary mechanistic investigations indicate that an outer‐sphere mode of substrate–catalyst interactions probably dominates the catalysis. 相似文献
946.
Yang Yang Tao Jia Ying‐Zi Han Zi‐Ang Nan Shang‐Fu Yuan Feng‐Lei Yang Di Sun 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2019,131(35):12408-12413
The hardness of oxo ions (O2?) means that coinage‐metal (Cu, Ag, Au) clusters supported by oxo ions (O2?) are rare. Herein, a novel μ4‐oxo supported all‐alkynyl‐protected silver(I)–copper(I) nanocluster [Ag74?xCuxO12(PhC≡C)50] ( NC‐1 , avg. x=37.9) is characterized. NC‐1 is the highest nuclearity silver–copper heterometallic cluster and contains an unprecedented twelve interstitial μ4‐oxo ions. The oxo ions originate from the reduction of nitrate ions by NaBH4. The oxo ions induce the hierarchical aggregation of CuI and AgI ions in the cluster, forming the unique regioselective distribution of two different metal ions. The anisotropic ligand coverage on the surface is caused by the jigsaw‐puzzle‐like cluster packing incorporating rare intermolecular C?H???metal agostic interactions and solvent molecules. This work not only reveals a new category of high‐nuclearity coinage‐metal clusters but shows the special clustering effect of oxo ions in the assembly of coinage‐metal clusters. 相似文献
947.
Zhu Mao Yutong Ye Haiming Lv Xiao Xia Han Yeonju Park Libin Zang Bing Zhao Young Mee Jung 《Angewandte Chemie (International ed. in English)》2020,59(27):10780-10784
Interfaces play an important role in enhancing the energy conversion performance of dye‐sensitized solar cells (DSCs). The interface effects have been studied by many techniques, but most of the studies only focused on one part of a DSC, rather than on a complete solar cell. Hence, monitoring the interface evolution of a DSC is still very challenging. Here, in situ/operando resonance Raman (RR) spectroscopic analyses were carried out to monitor the dynamics of the photovoltaic conversion processes in a DSC. We observed the creation of new species (i.e., polyiodide and iodine aggregates) in the photosensitization process. We also obtained molecular‐scale dynamic evidence that the bands from the C=C and C=N bonds of 2,2′‐bipyridyl (bpy), the S=C=N bonds of the NCS ligand, and photochemical products undergo reasonably strong intensity and frequency changes, which clearly demonstrates that they are involved in charge separation. Furthermore, RR spectroscopy can also be used to quickly evaluate the performance of DSCs. 相似文献
948.
Shengbo Zhang Meng Jin Tongfei Shi Miaomiao Han Qiao Sun Yue Lin Zhenhua Ding Li Rong Zheng Guozhong Wang Yunxia Zhang Haimin Zhang Huijun Zhao 《Angewandte Chemie (International ed. in English)》2020,59(32):13423-13429
Single‐atom catalysts have demonstrated their superiority over other types of catalysts for various reactions. However, the reported nitrogen reduction reaction single‐atom electrocatalysts for the nitrogen reduction reaction exclusively utilize metal–nitrogen or metal–carbon coordination configurations as catalytic active sites. Here, we report a Fe single‐atom electrocatalyst supported on low‐cost, nitrogen‐free lignocellulose‐derived carbon. The extended X‐ray absorption fine structure spectra confirm that Fe atoms are anchored to the support via the Fe‐(O‐C2)4 coordination configuration. Density functional theory calculations identify Fe‐(O‐C2)4 as the active site for the nitrogen reduction reaction. An electrode consisting of the electrocatalyst loaded on carbon cloth can afford a NH3 yield rate and faradaic efficiency of 32.1 μg h?1 mgcat.?1 (5350 μg h?1 mgFe?1) and 29.3 %, respectively. An exceptional NH3 yield rate of 307.7 μg h?1 mgcat.?1 (51 283 μg h?1 mgFe?1) with a near record faradaic efficiency of 51.0 % can be achieved with the electrocatalyst immobilized on a glassy carbon electrode. 相似文献
949.
Zexi Liu Jing Ai Prashant Kumar Enming You Xiong Zhou Xi Liu Zhongqun Tian Petr Bou Yingying Duan Lu Han Nicholas A. Kotov Songyuan Ding Shunai Che 《Angewandte Chemie (International ed. in English)》2020,59(35):15226-15231
A surface‐enhanced Raman scattering‐chiral anisotropy (SERS‐ChA) effect is reported that combines chiral discrimination and surface Raman scattering enhancement on chiral nanostructured Au films (CNAFs) equipped in the normal Raman scattering Spectrometer. The CNAFs provided remarkably higher enhancement factors of Raman scattering (EFs) for particular enantiomers, and the SERS intensity was proportional to the enantiomeric excesses (ee) values. Except for molecules with mesomeric species, all of the tested enantiomers exhibited high SERS‐ChA asymmetry factors (g), ranging between 1.34 and 1.99 regardless of polarities, sizes, chromophores, concentrations and ee. The effect might be attributed to selective resonance coupling between the induced electric and magnetic dipoles associated with enantiomers and chiral plasmonic modes of CNAFs. 相似文献
950.
Fang-Hua Zhao Zhong-Lin Li Shu-Fang Zhang Jian-Hui Han Mei Zhang Jun Han Yu-Wen Lin Jin-Mao You 《Acta Crystallographica. Section C, Structural Chemistry》2020,76(2):148-158
Two new metal–organic frameworks (MOFs), namely, three‐dimensional poly[diaquabis{μ2‐1,4‐bis[(2‐methyl‐1H‐imidazol‐1‐yl)methyl]benzene}bis(μ2‐glutarato)dinickel(II)] monohydrate], {[Ni2(C5H6O4)2(C16H18N4)2(H2O)2]·H2O}n or {[Ni2(Glu)2(1,4‐mbix)2(H2O)2]·H2O}n, ( I ), and two‐dimensional poly[[{μ2‐1,4‐bis[(2‐methyl‐1H‐imidazol‐1‐yl)methyl]benzene}(μ2‐glutarato)zinc(II)] tetrahydrate], {[Zn(C5H6O4)(C16H18N4)]·4H2O}n or {[Zn(Glu)(1,4‐mbix)]·4H2O}n ( II ), have been synthesized hydrothermally using glutarate (Glu2?) mixed with 1,4‐bis[(2‐methyl‐1H‐imidazol‐1‐yl)methyl]benzene (1,4‐mbix), and characterized by single‐crystal X‐ray diffraction, IR and UV–Vis spectroscopy, powder X‐ray diffraction, and thermogravimetric and photoluminescence analyses. NiII MOF ( I ) shows a 4‐connected 3D framework with point symbol 66, but is not a typical dia network. ZnII MOF ( II ) displays a two‐dimensional 44‐ sql network with one‐dimensional water chains penetrating the grids along the c direction. The solid‐state photoluminescence analysis of ( II ) was performed at room temperature and the MOF exhibits highly selective sensing toward Fe3+ and Cr2O72? ions in aqueous solution. 相似文献