High performance of nitrogen-doped carbon-supported cobalt catalyst for the mild and selective synthesis of primary amines

A nitrogen-doped carbon-supported Co catalyst (Co/N-C-800) was discovered to be highly active for the reductive amination of carbonyl compounds with NH₃ and the hydrogenation of nitriles into primary amines using H₂ as the hydrogen source. Structurally diverse carbonyl compounds were selectively transformed into primary amines with good to excellent yields (82.8–99.6%) under mild conditions. The Co/N-C-800 catalyst showed comparable or better catalytic performance than the reported noble metal catalysts. The Co/N-C-800 catalyst also showed high activity for the hydrogenation of nitriles, affording the corresponding primary amines with high yields (81.7–99.0%). An overall reaction mechanism is proposed for the reductive amination of benzaldehyde and the hydrogenation of benzonitrile, which involves the same intermediates of phenylmethanimine and N-benzylidenebenzylamine.     

Preparation of polymer-protected Pt/Co bimetallic colloid and its catalytic properties in selective hydrogenation of cinnamaldehyde to cinnamyl alcohol

A polymer-protected Pt/Co bimetallic colloid with a molar ratio of 3:1 has been prepared by a polyol process. Over the above Pt/Co bimetallic colloid catalyst, cinnamaldehyde can be selectively hydrogenated to cinnamyl alcohol with 99.8% selectivity at 96.2% conversion.     

空心微米镍球的表面改性及微波吸附性能研究

采用特殊的化学镀方法对已制备的空心微米镍球进行表面组装, 成功地在该镍球表面包覆了一层蜂窝状包覆钴层. 通过FESEM, TEM, XRD衍射表征了该包覆镍球, 观察到均匀包覆钴层的网眼构造和密集孔隙结构. 用BET气体吸附法、同轴线法对该镍球比表面积和微波性能进行了研究. 研究表明, 蜂窝状包覆钴层提高了粒子的比表面积, 同时表面镀钴提高了镍球的复介电常数值, 从而能增加粒子对电磁波的电介质损耗, 提高粒子在微波频率范围内对电磁波的反射吸收.     

射频等离子制备石墨烯负载Co3O4催化剂及其析氧性能研究

氢能的引入能有效提升配电网的供电可靠性,而电解水制氢是实现低碳转型的关键技术,开发高效的电解水催化剂势在必行。过渡金属氧化物储量大、催化活性高,是具有广阔应用前景的析氧反应催化剂。本文通过射频等离子体处理制备石墨烯上负载Co₃O₄析氧催化剂,XRD、Raman和XPS测试结果显示,二维结构石墨烯的引入加速表面电子迁移,增大了反应面积。等离子体处理促进了纳米粒子在石墨烯上的负载,利用等离子体刻蚀作用在催化剂表面制造出大量碳结构缺陷和氧空位结构,改善了活性位点分布,有效调控Co₃O₄电子结构,提高析氧催化活性。电化学测试表明,本文中合成的Co₃O₄@rGO在电流密度为50 mA·cm^-2时的过电位为410 mV,动力学反应速率较快,表现出优于商业IrO₂的析氧催化活性。     

两个基于2,5-二甲氧基对苯二甲酸和咪唑衍生物的超分子钴配位聚合物的结构及光催化反应

本文以咪唑衍生物为配体,通过水热合成法与钴离子制备出两个配位聚合物:{[Co(DTA)(1,4-DIB)(H₂O)]·H₂O}_n(1)和[Co(DTA)(1,3-BMIB)]_n(2)(1,4-DIB=1,4-二(1H-咪唑-1-基)苯; 1,3-BMIB=1,3-二(4-甲基-1H-咪唑-1-基)苯;H₂DTA=2,5-二甲氧基对苯二甲酸)。利用X射线单晶衍射、粉末衍射、热失重、元素分析、红外光谱以及固体紫外-可见光谱等对两个配合物进行了表征。结构分析证实配合物1和2是通过二维结构堆积成的三维超分子化合物。粉末衍射测试则显示两个配合物在水中有很好的稳定性。固体紫外-可见光谱显示两个配合物属半导体材料,对紫外-可见光有很强的吸收作用。在光催化实验中,配合物1和2可加快亚甲基蓝的降解速度。     

Microscopic origin of asymmetric magnetization reversal of Co/Pt multilayers with perpendicular magnetic anisotropy

We have comprehensively investigated asymmetric magnetization reversal behaviors of (x-Å Co/7.7 Å Pt)₅ multilayers (x = 3.1 and 4.7) with perpendicular magnetic anisotropy. Our direct observation of magnetic domain structures by means of magneto-optical microscopy reveals that the asymmetry arises both from nucleation and wall-motion processes. An asymmetric nucleation behavior is observed, which could be originated from the preexisting non-reversed domains which might have a reproducible or random spatial distribution, controllable by tuning the field profile. An asymmetric wall-motion behavior stemming from asymmetric stripe domain evolution is also observed.     

Effect of preparation methods on Co/ZrO2 catalysts in Fischer–Tropsch synthesis

Cobalt was incorporated into the zirconia support by different methods. The reducibility and activity of the catalysts was directly related to the preparation methods. Impregnated Co/ZrO₂ catalyst showed the highest reduction degree and the highest CO hydrogenation activity.     

Cu离子A位掺杂对LaSrCoO4复合氧化物氧化性能的影响

采用聚丙烯酰胺法制备了La1-xCuxSrCoO4(x=0.2-0.8)复合氧化物,考察了Cu离子掺杂量(x)对CO及C3H8氧化反应活性的影响,并运用XRD、IR、TPR和TPD等多种手段对复合氧化物催化剂进行了表征。结果表明,催化剂活性随x的变化而变化,Cu部分取代A位La能提高LaSrCoO4催化剂的CO及C3H8氧化反应活性,当x=0.4时La1-xCuxSrCoO4催化剂的晶格氧和Co3 含量较多,晶格氧的活动性较高,催化活性最佳。     

LixNi0.5Co0.5O2的态密度计算及电化学性能研究

>为获得综合性能更好的锂离子二次电池正极材料, 分析了Co掺杂对Li_xNiO₂电化学性能的影响. 采用密度泛函DFT理论对Li_xNiO₂和Li_xNi_0.5Co_0.5O₂的平均放电电压和态密度进行了计算. 同时, 用共沉淀法制备了Li_xNiO₂和Li_xNi_0.5Co_0.5O₂锂离子二次电池正极材料, 并对其进行了XRD结构分析和恒流充放电测试. 实验和计算结果表明: 随锂离子嵌入正极(电池放电), 电池的电压逐渐降低, 材料的态密度峰向低能量方向移动; 与Li_xNiO₂相比, Li_xNi_0.5Co_0.5O₂的电压平台相对较高(当0.25≤x≤0.5), 而且在Li^＋嵌/脱时, Li_xNi_0.5Co_0.5O₂的结构变化相对较小; Co离子的掺入, 减小了NiO₆八面体的畸变度, 使材料的电化学稳定性得以提高. 在钴掺杂镍酸锂体系中, NiO₆和CoO₆具有相互的稳定作用.     

Modified Ceria-Zirconia Fluorite-Like Catalysts for the Combustion of Methane

For dispersed ceria-zirconia-based solid solutions prepared via the polymerized complex method and annealed at 700℃, effects of bulk doping by Ca, Mn, Co, Bi or Nb cations and surface modification by Mn and Pt on their structural features, surface/bulk oxygen reactivity and catalytic activity in methane combustion are considered. With up to 20 mol% doping, a structural type of homogeneous solid solutions of anion-deficient fluorite with disordered anion vacancies is formed. Doping by transition metal cations or Pt increases the mobility and reactivity of the surface/bulk oxygen. A broad variation in specific rates of methane combustion for the studied systems was observed, suggesting structural sensitivity of this reaction. In general, there is no universal relationship between the oxygen mobility, the reactivity and the catalytic activity in methane combustion, which is explained by the factor of specific methane activation on surface active sites. For the Pt-promoted samples, Pt efficiency in methane activation depends on the Pt-support interaction, and the most favorable ones being mixed Pt/MnOx and Pt/NbOx clusters on the surface of the supports that exhibit high lattice oxygen mobilities.