NixCo0.85-xSe中空纳米球的溶液化学法合成、双功能特性及锌空电池应用（英文）

合成高活性、低成本、双功能特性的电催化剂是目前发展新能源材料的重要任务.过渡金属硒化物具有较高的电导特性、可调节的物理化学特性等,成为了开发高效氧还原和氧析出催化剂的研究热点.本文采用多元醇溶液化学法合成了具有较大比表面积的NixCo0.85-xSe中空纳米球.该催化剂的ORR起始电位达到0.89 V,OER在10 mA cm^-2电流密度下的过电位达到305 mV.以NixCo0.85-xSe中空纳米球为空气电极、锌片为阴极组成的锌空电池具有良好的比容量和循环稳定性.NixCo0.85-xSe中空纳米球优异的催化性能主要归因于较大的比表面积、Ni和Co的协同催化特性以及良好的导电性.本文为设计高效的锌空电池催化剂提供了良好的理论基础和实验支持.     

Small-sized tungsten nitride anchoring into a 3D CNT-rGO framework as a superior bifunctional catalyst for the methanol oxidation and oxygen reduction reactions

The application of direct methanol fuel cells (DMFC) is hampered by high cost, low activity, and poor CO tolerance by the Pt catalyst. Herein, we designed a fancy 3D hybrid by anchoring tungsten nitride (WN) nanoparticles (NPs), of about 3 nm in size, into a 3D carbon nanotube-reduced graphene oxide framework (CNT-rGO) using an assembly route. After depositing Pt, the contacted and strongly coupled Pt–WN NPs were formed, resulting in electron transfer from Pt to WN. The 3D Pt–WN/CNT-rGO hybrid can be used as a bifunctional electrocatalyst for both methanol oxidation reaction (MOR) and oxygen reduction reaction (ORR). In MOR, the catalysts showed excellent CO tolerance and a high mass activity of 702.4 mA·mg_Pt ^–1, 2.44 and 3.81 times higher than those of Pt/CNT-rGO and Pt/C(JM) catalysts, respectively. The catalyst also exhibited a more positive onset potential (1.03 V), higher mass activity (151.3 mA·mg_Pt ^–1), and better cyclic stability and tolerance in MOR than ORR. The catalyst mainly exhibited a 4e-transfer mechanism with a low peroxide yield. The high activity was closely related to hybrid structure. That is, the 3D framework provided a favorable path for mass-transfer, the CNT-rGO support was favorable for charge transfer, and strongly coupled Pt–WN can enhance the catalytic activity and CO-tolerance of Pt. Pt–WN/CNT-rGO represents a new 3D catalytic platform that is promising as an electrocatalyst for DMFC because it can catalyze both ORR and MOR in an acidic medium with good stability and highly efficient Pt utilization.

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The use of a dynamic hydrogen electrode as an electrochemical tool to evaluate plasma activated carbon as electrocatalyst support for direct methanol fuel cell

The objectives of this study were to functionalize the carbon black surface by chemically introducing oxygenated groups using plasma technology. This should enable a better interaction of the carbon support with the metallic catalyst nanoparticles, hindering posterior support particle agglomeration and preventing loss of active surface. PtRu/C nanoparticles were anchored on the carbon supports by the impregnation method and direct reduction with hydrazine. Physical characterization of the materials was carried out using energy dispersive X-ray analysis and transmission electron microscopy. The screen printing technique was used to produce membrane electrode assemblies for single cell tests in methanol/air (DMFC). Tests were carried out using the dynamic hydrogen electrode as an electrochemical tool to evaluate the anode and cathode behavior separately.     

Organic-acid-assisted synthesis of a 3D lasagna-like Fe-N-doped CNTs-G framework: An efficient and stable electrocatalyst for oxygen reduction reactions

The scalable preparation of multi-functional three-dimensional (3D) carbon nanotubes and graphene (CNTs-G) hybrids via a well-controlled route is urgently required and challenging.Herein,an easily operated,oxalic acid-assisted method was developed for the in situ fabrication of a 3D lasagna-like Fe-N-doped CNTs-G framework (LMFC) from a precursor designed at the molecular level.The well-organized architecture of LMFC was constructed by multi-dimensionally interconnected graphene and CNTs which derived from porous graphene sheets,to form a fundamentally robust and hierarchical porous structure,as well as favorable conductive networks.The impressive oxygen reduction reaction (ORR) performances in both alkaline and acidic conditions helped confirm the significance of this technically favorable morphological structure.This product was also the subject of research for the exploration of decisive effects on the performance of ORR catalysts with reasonable control variables.The present work further advances the construction of novel 3D carbon architectures via practical and economic routes.     

CoSeO3化合物的制备及对阴极氧还原的催化性能

以Co₄(CO)₁₂和Se为原料, 采用低温回流方法在乙二醇介质中合成了CoSeO₃化合物。利用扫描电镜(SEM)、X射线衍射仪(XRD)和旋转圆盘电极(RDE)技术表征合成的化合物微观形貌、结构特征和电化学性能。这种化合物主要由单斜结构的CoSeO₃•H₂O晶粒组成, 粒径大小约为26.7 nm, 具有规则的晶体外形。在25℃, 0.5 mol/L H₂SO₄电解液中, CoSeO₃化合物对氧还原反应(ORR)表现出明显的电催化活性, 开路电位为0.80 V(vs NHE)。根据Koutecky-Levich方程计算出每个氧分子还原过程转移的电子数约为3.8。在0.64~0.76 V(vs NHE)电位范围内, 测得催化剂的传递系数、Tafel斜率和交换电流密度分别为0.50、119 mV和1.98×10^-6 mA/cm²。CoSeO₃化合物的催化活性和电化学稳定性也与商品Pt催化剂进行了比较。