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1.
生物质基碳材料作为氧还原反应催化剂的研究进展 总被引:1,自引:0,他引:1
燃料电池作为一种清洁能源有很大的发展前景,其阴极氧还原反应多采用铂基催化剂,但由于贵金属铂的储量稀少、价格昂贵等原因,严重阻碍了燃料电池的商业化进程。寻找高活性、高稳定性的新材料来替代阴极铂基催化剂成为燃料电池大规模商业化亟待解决的关键问题之一。研究表明,以生物质为原料的碳材料有望成为商业铂基氧还原催化剂的一种理想替代品。本文综述了这方面的研究进展,并且展望了未来的发展趋势。 相似文献
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硝基苯催化还原羰基化为苯氨基甲酸乙酯 总被引:3,自引:1,他引:3
研究了几种含氮杂环配体的钯配合物或其相应的混合物在硝基苯还原羰基化为苯氨基甲酸酯反应中的催化性能。结果表明,钯-邻菲啰啉配合物在该反应中具有最高的催化活性,且钯配合物或钯盐的阴离子性质对生成苯氨基甲酸酯的选择性有很大的影响。从反应结果推测,在反应条件下可能形成两种不同价态钯的配合物,其中零价钯配合物是硝基苯的还原中心,而二价钯配合物为还原羰基化中心。电化学循环伏安法测试结果表明,吡啶、邻菲啰啉等配体对稳定Pd(Ⅱ)氧化态具有重要作用。 相似文献
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硝基苯在不同的还原剂及不同的介质中可以被还原成亚硝基苯、苯胲、偶氮苯、氧化偶氮苯、氢化偶氮苯等不同产物。这一性质深刻揭示了还原剂的还原能力除了与本身的性质有关之外,还与反应介质密切相关。由于这些还原产物结构复杂,相应反应的机理在国内外常见经典有机化学教科书中鲜有描述,给初学者的学习理解造成了困难。本文从氧化还原反应中电子守恒原理出发,探讨了这一组还原反应的可能机理,并导出了完整的化学反应方程式。 相似文献
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天然高分子负载双金属催化剂催化硝基苯还原羰化反应 总被引:2,自引:0,他引:2
天然生物高分子材料-壳聚糖(简写为CS)负载催化刑:Si02—CS—PdCl2,利用Pd-Ni双金属协同效应和高分子载体对催化活性物种的保护,在催化硝基苯的还原碳化反应中表现出了较高的催化活性和选择性.并且尝试了催化刑的重复使用. 相似文献
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硝基苯的电还原特性研究 总被引:14,自引:0,他引:14
采用准稳态极化、循环伏安、线性扫描和恒电位阶跃等测试方法,对H2SO4溶液中硝基苯的电还原特性进行研究,评价了硝基苯在Cu、Cu-Hg和Cu-Ni电极的电还原反应活性,研究了硝基苯电还原为PAP的中间步骤,并对反应机理进行了探讨。结果表明,硝基苯在酸性介质中的电还原反应存在中间步骤,并伴有反应物吸附现象,硝基苯电还原反应受硝基苯及其还原产物在溶液中的液相传质步骤控制. 相似文献
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目前,开发高效的阴极氧还原反应(ORR)电催化剂是实现燃料电池和金属-空气电池商业化发展急需完成的目标。在过去的几十年中,人们在探索廉价高效的 ORR电催化剂(如 N掺杂的非金属及非铂电催化剂)领域做了广泛的研究。在 N掺杂的碳基 ORR催化剂中,已知的 N基活性位点主要分为四类,即吡啶类氮(P-N)、吡咯类氮(Py-N)、石墨化氮(G-N)和氧化类氮(O-N)。尽管人们对这四种类型氮的活性位点做了大量的研究,但是它们在催化反应中起到的 ORR催化作用以及催化机理和活性位点本身结构的关系仍不够明确。早期的研究中有人认为 P-N或者 Py-N是 ORR催化活性位点,也有人认为是 G-N起作用。最近也有研究表明, P-N和 G-N都是 ORR催化活性位点,只是在 ORR中所起的催化能力不同。因此,很有必要认清这些问题。
本文通过 Hummer法酸性氧化一次和两次碳黑 Vulcan XC-72(VXC-72)以及随后高温热处理,制备了一系列 ORR催化剂 VXCO-1, VXCO-2, VXCO-1(900)和 VXCO-2(900),采用场发射扫描电子显微镜(SEM), N2吸附脱附法,元素分析仪(EA), X射线光电子能谱(XPS),拉曼光谱仪(Raman), X射线衍射能谱(XRD),电化学循环伏安法和线性伏安法测试等手段研究 Hummers法酸氧化和高温热处理对 VXC-72形貌组成的影响,以及这些碳基中成分和其催化 ORR能力的关系。
SEM结果表明, Hummer法酸性氧化处理 VXC-72一次和两次后可以逐层剥落其最外边的碳层结构,最终得到表面光滑的类片层状结构的碳材料(VXCO-1和 VXCO-2)。这种表面光滑的类片层状结构的碳材料比表面积大于处理前的 VXC-72,而高温热处理之后的碳材料(VXCO-1(900)和 VXCO-2(900))由于类石墨层碎片结构蒸发损失暴露出更多内部的微孔和介孔结构使比表面积增加。 Raman和 XRD结果表明,氧化处理使碳材料的石墨化程度增加,而高温热处理则降低了其石墨化程度。
EA和 XPS结果表明, Hummer法酸性氧化处理可以使在碳材料中掺入的 N以石墨化的为主,高温热处理却使得石墨化氮转变为吡啶类的氮。 ORR结果发现,活性的石墨化氮倾向于使 ORR反应经历两电子过程,从而生成 H2O2为主要产物;而吡啶类氮的活性位点更倾向于使 ORR反应经过四电子过程,主产物是水。该结果有助于新型碳基氧还原催化剂的设计和分析。 相似文献
本文通过 Hummer法酸性氧化一次和两次碳黑 Vulcan XC-72(VXC-72)以及随后高温热处理,制备了一系列 ORR催化剂 VXCO-1, VXCO-2, VXCO-1(900)和 VXCO-2(900),采用场发射扫描电子显微镜(SEM), N2吸附脱附法,元素分析仪(EA), X射线光电子能谱(XPS),拉曼光谱仪(Raman), X射线衍射能谱(XRD),电化学循环伏安法和线性伏安法测试等手段研究 Hummers法酸氧化和高温热处理对 VXC-72形貌组成的影响,以及这些碳基中成分和其催化 ORR能力的关系。
SEM结果表明, Hummer法酸性氧化处理 VXC-72一次和两次后可以逐层剥落其最外边的碳层结构,最终得到表面光滑的类片层状结构的碳材料(VXCO-1和 VXCO-2)。这种表面光滑的类片层状结构的碳材料比表面积大于处理前的 VXC-72,而高温热处理之后的碳材料(VXCO-1(900)和 VXCO-2(900))由于类石墨层碎片结构蒸发损失暴露出更多内部的微孔和介孔结构使比表面积增加。 Raman和 XRD结果表明,氧化处理使碳材料的石墨化程度增加,而高温热处理则降低了其石墨化程度。
EA和 XPS结果表明, Hummer法酸性氧化处理可以使在碳材料中掺入的 N以石墨化的为主,高温热处理却使得石墨化氮转变为吡啶类的氮。 ORR结果发现,活性的石墨化氮倾向于使 ORR反应经历两电子过程,从而生成 H2O2为主要产物;而吡啶类氮的活性位点更倾向于使 ORR反应经过四电子过程,主产物是水。该结果有助于新型碳基氧还原催化剂的设计和分析。 相似文献
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这里发现锰化合物能够催化芳香碳-氧键的还原断裂.就我们所知,目前还没有锰催化芳香碳-氧键断裂方面的报道.以二苯并呋喃为底物,对各种反应条件进行优化,得到的较佳反应条件为5% Mn(OAc)2,3当量Li-A1H4,140 ℃温度,四氢呋喃溶剂.在这个反应条件下,多种芳香碳-氧键能够发生还原断裂.甲醇钠的添加能够有效地促进二苯醚等底物的反应.对反应机理进行了初步研究,结果表明反应可能经历自由基过程. 相似文献
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硝基苯还原羰化反应制备氨基甲酸酯选择性的研究 总被引:4,自引:0,他引:4
在硝基苯还原羰化反应和还原反应的竞争中,使用高分了载体,加人第二金属 组分,升高反应温度有利于还原羰化反应的进行.并且实现了利用双金属效应,在 不含有机配体的体系中高选择性地进行硝基苯还原羰化反应. 相似文献
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《Journal of Coordination Chemistry》2012,65(15):1719-1728
Catalytic activity for reduction of nitrobenzene to aniline (98%) and azobenzene (2%) using a poly(4-vinylpyridine)-immobilized Cu catalyst [Cu(II)/P(4-VP)] under a CO atmosphere in aqueous 2-ethoxyethanol was studied as a function of the various reaction parameters ([Cu], P(CO), T, and nitrobenzene/Cu molar ratio). Reaction rates were first-order in [Cu]tot over 1.0–12.0?wt.% range and in P(CO) over the 6.8–27.2?atm range. The catalytic activity proved to be non-linear in nitrobenzene/Cu ratio over 41–500 molar ratio range. These results suggest that the rate-limiting step is preceded by reversible coordination of nitrobenzene to a carbonyl–Cu(I) immobilized species. A catalytic mechanism consistent with the data is proposed. 相似文献
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LI Hui ZHAO Yong-sheng ZHAO Ran MA Bai-wen CHEN Zi-fang SU Yan ZHOU Rui 《高等学校化学研究》2013,29(4):765-770
Sucrose-modified nanoscale zero-valent iron(SM-NZVI) was prepared with liquid phase reducing method, and characterized by transmission electron microscopy(TEM) and X-ray diffraction(XRD) for the shape and structure. The size of SM-NZVI particles was about 100―150 nm and they displayed better dispersity. The degradation of nitrobenzene(NB) in water by SM-NZVI was carried out in batch experiments. The results indicate that the efficiency of NB reduction via SM-NZVI increased by 44.24% compared with that via NZVI, and coexistent Ca2+, Mg2+, HCO3- and other ions showed little effect on NB reduction but negative influence on aniline(AN) production. Furthermore, the kinetic researches indicate that NB reduction with SM-NZVI could be described by pseudo first-order kinetic model at different initial pH values and iron dosage. The oxidation products of iron were mainly Fe3O4 and Fe2O3 with irregular shape. 相似文献
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Jie Chen Rong Ji Dai Bin Tong Sheng Yuan Xiao Wei Wei Meng 《中国化学快报》2007,18(1):10-12
The reduction of 4-nitrophenol catalyzed by nitroreductase in the presence of NADH was investigated in this paper.4-Amino- phenol and 4-bydroxylamino-phenol were found in the reductive products.The relationship between reaction time and the reductive ratio were studied.The similar reducing ratios of 4-nitrophenol were obtained under aerobic and anaerobic conditions.The results indicated that an oxygen-insensitive reaction was proceeded in the reduction of 4-nitrophenol and nitroreductase was an oxygen- insensitive enzyme.The reductive products of 4-nitrophenol were determined by HPLC and MS. 相似文献
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《中国化学快报》2020,31(10):2678-2682
In this work, the reduction of mercury ions (Hg2+) to elemental mercury (Hg0) was easily achieved using highly reductive carbon dots (r-CDs), which synthesized from sucrose by a simple and cost-effective method. After a careful mechanistic study, the reduction was probably accomplished with the large numbers of electrons contained in r-CDs rather than the oxidation of its functional groups. Additionally, a 3-(4,5-dimethylthiazol-2-yl)-2,5-diphenyltetrazolium bromide (MTT) assay showed that the r-CDs were nontoxic to wildlife and human beings. Consequently, the r-CDs were used as an alternative to toxic reductants (SnCl2 or NaBH4) for the sensitive and in situ determination of mercury by cold vapor generation (CVG) coupled to a miniature point discharge optical emission spectrometer (μPD-OES). Limit of detection of 0.05 μg/L was obtained for Hg2+, with relative standard deviation (RSD) less than 5.4% at a concentration of 5 μg/L. The accuracy of r-CDs induced CVG-μPD-OES was validated by the determination of mercury in a certified reference material (DOLT-5, dogfish liver) and five natural water samples collected from different rivers and lakes in Chengdu City. Since r-CDs are nontoxic and prepared from abundant and inexpensive sucrose, the r-CDs induced CVG-μPD-OES retains the great potential for the inexpensive and environmentally friendly field analysis of mercury in natural water. The accuracy of the proposed method was validated by the analysis of a certified reference material and several water samples with satisfactory results. 相似文献
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Yang Yang Ngoc Duy Pham Disheng Yao Huaiyong Zhu Prasad Yarlagadda Hongxia Wang 《中国化学快报》2018,29(8):1242-1250
Incorporation of proper inorganic p-type semiconductors as hole transport layer has great potential to increase long-term stability while maintaining high power conversion efficiency of perovskite solar cells with low material cost. 相似文献
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Novel Pt nanoparticles (PN) ensemble on macroporous carbon (MPC) hybrid nanocomposites (PNMPC) were prepared through a rapidly and simple one-step microwave-assisted heating procedure. The obtained PNMPC was characterized by transmission electron microscopy (TEM), X-ray photoelectron spectroscopy (XPS), thermogravimetric analysis (TGA) and electrochemical methods. The electrochemical reduction of nitrobenzene (NB) was thoroughly investigated at the PNMPC modified glassy carbon (GC) electrode, and the catalytic rate constant was calculated to be 3.14 × 104 M−1 s−1 for NB. A sensitive NB sensor was developed based on the PNMPC/GC electrode, which showed a wide linear range (1–200 μM), low detection limit (50 nM), high sensitivity (6.93 μA μM−1), excellent anti-interference ability and good stability. And moreover, the electrode was successfully applied to the determination of NB in real samples. 相似文献
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Samuel Piña Jr. Diana M. Cedillo Carlos Tamez Nezhueyotl Izquierdo Jason G. Parsons Jose J. Gutierrez 《Tetrahedron letters》2014
Reported here is the reduction of aromatic nitro compounds using sodium borohydride and transition metal sulfides as catalysts. The reaction conditions were optimized using the reduction of nitrobenzene as a model reaction. The catalysts studied were iron sulfide (Fe3S4), copper sulfide (CuS), zinc sulfide (ZnS), cobalt sulfide (Co3S4), and nickel sulfide (NiS). The reduction was monitored using gas chromatography. Quantitative conversions were achieved using Co3S4 and NiS, representing a ten-fold increase in reactivity compared to the non-catalyzed reaction. Fe3S4 and ZnS had no apparent effect on the reduction of nitrobenzene while the reduction using CuS showed a marginal increase. The reduction method was applied to several aryl-nitro derivatives containing either electron-withdrawing or electron-donating groups. Halogen containing aryl-nitro compounds were reduced without dehalogenation. The reduction had no effect on other functional groups such as carboxylic acids, esters, amides, or alkenes, indicating that the reduction is highly chemoselective. 相似文献
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活性炭酸处理对CuO/C催化剂上NO还原反应的影响 总被引:3,自引:0,他引:3
4种国产活性炭被用于NO还原反应,其中,山楂核炭和山桃核炭具有较高的NO还原转化率。实验发现,表面含氧基团-COO-对活性炭自身的还原性和对NO的还原活性有很重要的影响。对表面富-COO-基团的活性炭,稀盐酸处理使表面-COO-显著分解。 相似文献