Co3xCu3-3x(PO4)2 microspheres,a novel non-precious metal catalyst with superior catalytic activity in hydrolysis of ammonia borane for hydrogen production

Development of robust and cheap catalyst for fast hydrogen evolution from ammonia borane (AB) aqueous solution is an interesting and important topic in the field of hydrogen energy. Herein, a novel non-precious Co_3xCu_3-3x(PO₄)₂ catalyst possessing high reactivity in AB hydrolysis has been developed for the first time. By tuning the molar ratio of Co and Cu, a series of Co_3xCu_3-3x(PO₄)₂ with different x were synthesized and the catalytic behavior in AB hydrolysis was examined. At the optimal x of 0.8, an ultrahigh turnover frequency of 72.6 min⁻¹ was achieved. Additionally, the synergistic effect between Cu₃(PO₄)₂ and Co₃(PO₄)₂ was experimentally confirmed, and the reaction kinetics of AB hydrolysis catalyzed by Co_2.4Cu_0.6(PO₄)₂ were investigated. This work provides a simple route and some new insights for the fabrication of a cheap P-containing catalyst with robust catalytic performance.     

超高压调节酶催化功能及其作用机制

在酶学领域中,超高压和温度类似,作为一种物理学方法,可以用来调节酶催化功能,促使酶的构象发生变化。对超高压调节酶催化功能的原理、影响酶构象的作用机制,以及一些新型研究方法等进行了综述。展望了此项新技术的发展前景。     

Synthesis,Characterization, and Catalytic Activity of Mn‐doped Perovskite Oxides for Three‐Way Catalysis

Mn‐doped La_0.8Sr_0.2CoO₃ perovskite oxides (La_0.8Sr_0.2Co_1–xMn_xO₃; x = 0, 0.1, 0.3, 0.5) were synthesized by a modified sol‐gel method. The phase‐pure oxides were obtained. CoO and carbonates were formed on the surface of La_0.8Sr_0.2CoO₃. With increasing doping content, these impurities were reduced while the stability of the perovskite structure was improved. The valence state of B‐site ions and the amount of absorbed oxygen were influenced by Mn doping. The catalytic activity of the perovskite catalysts was investigated for CO oxidation and simultaneous removal of CO, C₃H₈, and NO. For CO and NO removal, La_0.8Sr_0.2Co_0.9Mn_0.1O₃ exhibited the best performance. For C₃H₈ removal, the reactivity was promoted linearly with the doping content. The structure‐activity relationship is also discussed.     

多级孔HZSM-5分子筛催化快速热解生物质制芳烃

采用酸和/或碱处理法制备了一系列多级孔HZSM-5分子筛，采用XRD、N₂吸附、XRF、TEM、²⁷Al MAS NMR和NH₃-TPD等表征手段对其孔道结构和酸性进行表征。表征结果表明，采用碱处理方法，可获得孔径集中于3~6 nm的介孔结构，通过改变酸、碱处理次序，可调变酸中心数量和强酸/总酸中心比例。在Py-GC/MS装置上，以纤维素和水稻秸秆为原料，研究多级孔分子筛结构对催化快速热解（CFP）制芳烃反应的影响。反应评价结果表明，同商品级HZSM-5相比，采用先碱后酸处理获得的多级孔HZSM-5分子筛（HZ-OH/H），可将纤维素CFP芳烃碳产率由32.3%提高至43.6%，可将水稻秸秆CFP芳烃碳产率由23.0%提高至30.8%。多级孔HZ-OH/H分子筛的孔道结构和酸中心分布特征，对开发应用于生物质制芳烃的高效工业催化剂具有借鉴意义。     

电催化氮气还原合成氨催化材料研究进展

氨是纺织、制药、化肥等领域重要的化工原料，也是一种清洁的能源载体，需求量大。目前氨的工业生产主要为Haber-Bosch法，反应条件严苛，能源消耗大且碳排放较高。电催化氮气还原(NRR)合成氨是一种在常温常压下进行的反应，工作电位低，且电能可通过清洁能源提供，是一种很有潜力的合成氨新工艺。但目前电催化NRR材料的产氨速率和法拉第效率低、工作稳定性不够高、溶液中痕量氨的定量检测困难及检测标准不统一等都为其发展带来了巨大挑战。本文首先介绍了电催化NRR的反应机理和常用研究方法，然后重点梳理了2019年以来NRR催化材料的最新研究进展，最后对该领域研究面临的挑战和机遇进行了展望。     

NiMn2O4尖晶石氧化物阴极的制备及电化学性能研究

高性能阴极材料的开发对推动中温固体氧化物燃料电池（intermediate temperature solid oxide fuel cells, IT-SOFCs）的发展具有重要意义。本文采用溶胶-凝胶法制备了尖晶石型NiMn₂O₄（NMO）电子-离子混合导体材料，并作为IT-SOFCs阴极进行了系统的研究，通过X射线衍射表征确定NMO材料呈稳定的立方相结构，并采用电导弛豫方法对其氧离子传导能力进行了研究。发现NMO具有优秀的氧离子传导能力，为其电化学性能提供了保障。对称电池的电化学阻抗谱测试结果表明，800℃时NMO阴极材料的界面电阻值为0.27 Ω·cm^-2，同时作为阳极支撑型SOFC的阴极材料进行放电时的最大功率密度可以达到864.9 mW·cm^-2。上述结果表明，NiMn₂O₄是一种极具潜力的IT-SOFCs阴极材料。     

Single‐step synthesis of a radically polymerizable 1,1′‐bi‐2‐naphthol derivative for asymmetric catalysis

A new polymerizable 1,1′‐bi‐2‐naphthol derivative for polymer‐supported catalytic asymmetric synthesis is presented. The synthesis is conducted within a single reaction step, which is a major advantage over other approaches presented in the literature. The ligand‐bearing polymer is prepared through copolymerization with N‐isopropylacrylamide. Preliminary experiments on the utility in catalytic asymmetric alkylation reactions reveal the accessibility and activity of the polymer‐attached catalysts. The stereoselectivity of the reaction is found to be somewhat lower than for reactions performed in the presence of free 1,1′‐bi‐2‐naphthol, and thus requires further optimization. The enantiomeric excess of the reaction products was determined via ¹H NMR spectroscopy after chiral derivatization with (R)‐α‐methylbenzyl isocyanate. © 2015 Society of Chemical Industry     

TiO2上的CuAg纳米粒子用于高效乙醛光降解

光降解乙醛(CH3CHO)是一种新型高效的乙醛去除方法，通常采用TiO2作为光催化剂。然而TiO2对乙醛吸附能力较弱，对产物的选择性较低，电子-空穴对重组率较高，严重限制了对乙醛的降解性能。本研究通过在TiO2上负载CuAg纳米粒子(CuAg/TiO2)，成功构建了高效稳定的光催化降解乙醛催化剂，有效解决了TiO2的固有缺陷。在自然光照射下，CuAg/TiO2对乙醛的降解率高达42.49%。连续4轮全光谱光催化降解乙醛，CuAg/TiO2活性均保持在98.89%以上。进一步的机理研究表明，CuAg/TiO2中的CuAg纳米粒子在光照下产生热电子，随后热电子转移到TiO2和吸附在Ag位点上的氧中。CuAg/TiO2上生成的超氧自由基能有效地降解乙醛，从而在乙醛降解过程中表现出优异的性能。     

Spatially Resolved Characterization of the Gas Propagator in Monolithic Structured Catalysts Using NMR Diffusiometry

Gas diffusivity measurements in opaque porous media were performed using nuclear magnetic resonance. An optimized pulsed‐field gradient stimulated echo method with free volume selection was used to investigate the propagator of thermally polarized methane gas within commercial monolithic catalyst supports. Since signal losses due to T₂ relaxation were minimized by using a short echo time, diffusion processes could be characterized by the measured propagator functions and effective diffusion coefficients were determined for a broad range of observation times and in different spatial directions. The study of this noninvasive characterization of gas diffusion found a clear effect of the monolith type and its pore size and coating on the effective gas diffusion coefficient and the apparent tortuosity for a given observation time.