Synthesis of Pt-based and Pt-free fuel cell catalysts and their electrocatalytic performance

燃料电池（FuelCell）是一种将存在于燃料与氧化剂中的化学能直接转化为 电能的发电装置。燃料电池具有能量转化效率高、环境污染小和燃料适用范围 广等优点。催化剂是燃料电池研究的核心部件。铂基纳米材料是当前最通用的 催化剂。然而，铂基材料的高昂价格、相对较低的稳定性和活性仍然限制其广 泛应用。因而设计和合成高效的燃料电池催化剂是当前亟需的。本研究工作主 要针对提高铂基催化剂的活性、稳定性和选择性以及寻找高效的非铂催化剂开 展，主要工作内容如下： 1）采用超细铂纳米线制备了网状铂膜电极。该膜电极具有超高的比表面积， 能在生理条件催化葡萄糖氧化，可成功应用于无酶葡萄糖传感和葡萄糖/...Fuel cells as new electrochemical energy conversion devices have received much attention due to a variety of advantages, such as high energy efficiency, minimum environmental impact and abundant fuel supply. Pt-based catalysts are the most popular fuel cell catalysts, but their high cost, limited activity, and weak durability severely hinder their applicability to broad commercialization. The deve...学位：博士后院系专业：化学化工学院化学系_无机化学学号：201017002

Etching Growth under Surface Confinement: An Effective Strategy To Prepare Mesocrystalline Pd Nanocorolla

通讯作者地址: Zheng, NF (通讯作者),Xiamen Univ, Coll Chem & Chem Engn, State Key Lab Phys Chem Solid Surfaces, Xiamen 361005, Peoples R China 地址: 1. Xiamen Univ, Coll Chem & Chem Engn, State Key Lab Phys Chem Solid Surfaces, Xiamen 361005, Peoples R China 2. Xiamen Univ, Coll Chem & Chem Engn, Dept Chem, Xiamen 361005, Peoples R China 电子邮件地址: [email protected] etching growth strategy was developed to prepare corolla-like Pd mesocrystals consisting of unidirectionally aligned, well-spaced, and connected ultrathin (1.8-nm-thick) Pd nanosheets. The combined use of CO and Fe(3+) is critical to the successful synthesis of the branched corolla-like Pd mesocrystals. While CO functions as the surface-confining agent to allow anisotropic growth of the 1.8-nm-thick Pd nanosheets as branches, Fe(3+) etches the Pd seeds at the early stage of the reaction to induce formation of the branched structure. Inheriting the unique properties of 1.8-nm-thick Pd nanosheets, the as-prepared Pd mesocrystals display well-defined surface plasmon resonance absorption in the near-infrared region, a high electrochemically active surface area, and a significant photothermal effect when irradiated with a near-infrared laser. Owing to the presence of internal voids and increased apparent thickness, the Pd mesocrystals also exhibit several features superior to those of single-domain Pd nanosheets, making them promising for electrocatalysis and cancer photothermal therapy applications.NSFC 21131005 21021061 20925103 20871100 Fok Ying Tung Education Foundation 121011 MOST of China 2011CB932403 2009CB930703 NSF of Fujian Province 2009J06005 Key Scientific Project of Fujian Province 2009HZ0002-

Amine-Assisted Synthesis of Concave Polyhedral Platinum Nanocrystals Having {411} High-Index Facets

通讯作者地址: Zheng, NF (通讯作者), Xiamen Univ, State Key Lab Phys Chem Solid Surfaces, Xiamen 361005, Peoples R China 地址: 1. Xiamen Univ, State Key Lab Phys Chem Solid Surfaces, Xiamen 361005, Peoples R China 2. Xiamen Univ, Dept Chem, Coll Chem & Chem Engn, Xiamen 361005, Peoples R China 电子邮件地址: [email protected] surfaces of a face-centered cubic metal (e.g., Pd, Pt) have a high density of low-coordinated surface atoms and therefore possess enhanced catalysis activity in comparison with low-index faces. However, because of their high surface energy, the challenge of chemically preparing metal nanocrystals having high-index facets remains. We demonstrate in this work that introducing amines as the surface controller allows concave Pt nanocrystals having {411} high-index facets to be prepared through a facile wet-chemical route. The as-prepared Pt nanocrystals display a unique octapod morphology with {411} facets. The presence of high-index {411} exposed facets endows the concave Pt nanocrystals with excellent electrocatalytic activity in the oxidation of both formic acid and ethanol.NSFC 21021061 20925103 20923004 20871100 Fok Ying Tung Education Foundation 121011 MOST of China 2011CB932403 2009CB930703 NFFTBS J1030415 NSF of Fujian Province 2009J06005 Key Scientific Project of Fujian Province 2009HZ0002-

A graphene-platinum nanoparticles-ionic liquid composite catalyst for methanol-tolerant oxygen reduction reaction

通讯作者地址: Tan, YM (通讯作者),Xiamen Univ, State Key Lab Phys Chem Solid Surfaces, Xiamen 361005, Peoples R China 地址: 1. Xiamen Univ, State Key Lab Phys Chem Solid Surfaces, Xiamen 361005, Peoples R China 2. Xiamen Univ, Dept Chem, Coll Chem & Chem Engn, Xiamen 361005, Peoples R China 3. Hunan Normal Univ, Coll Chem & Chem Engn, Minist Educ China, Key Lab Chem Biol & Tradit Chinese Med Res, Changsha 410081, Hunan, Peoples R China 电子邮件地址: [email protected] report here that graphene-supported Pt nanoparticles impregnated with the ionic liquid [MTBD][bmsi] which is more oxygen-philic and less methanol-philic than the exterior aqueous solution can exhibit both enhanced electrocatalytic activity and excellent methanol tolerance for oxygen reduction reaction.MOST of China 2011CB932403 2009CB930703 NSF of China 21131005 21021061 20925103 Fok Ying Tung Education Foundation 121011 NSF of Fujian 2009J06005 China Postdoctoral Science Foundation 2010048071

Carbon Monoxide-Assisted Synthesis of Single-Crystalline Pd Tetrapod Nanocrystals through Hydride Formation

通讯作者地址: Zheng, NF (通讯作者),Xiamen Univ, State Key Lab Phys Chem Solid Surfaces, Coll Chem & Chem Engn, Xiamen 361005, Peoples R China 地址: 1. Xiamen Univ, State Key Lab Phys Chem Solid Surfaces, Coll Chem & Chem Engn, Xiamen 361005, Peoples R China 2. Xiamen Univ, Dept Chem, Coll Chem & Chem Engn, Xiamen 361005, Peoples R China 3. Xiamen Univ, Dept Phys, Xiamen 361005, Peoples R China 电子邮件地址: [email protected]; [email protected] monoxide can adsorb specifically on Pd(111) to induce the formation of unique Pd nanostructures. In the copresence of CO and H-2 single-crystalline Pd tetrapod nanocrystals have now been successfully prepared. The Pd tetrapods are enclosed by (111) surfaces and are yielded through hydride formation. Density functional theory calculations revealed that the formation of PdHx in the presence of H, reduces the binding energy of CO on Pd and thus helps to decrease the CO coverage during the synthesis, which is essential to the formation of the PdHx tetrapod nanocrystals. In addition to tetrapod nanocrystals, tetrahedral nanocrystals were also produced in the copresence of CO and H-2 when the reaction temperature was ramped to further lower the CO coverage. Upon aging in air, the as-prepared PdHx nanocrystals exhibited a shape-dependent hydrogen releasing behavior. The conversion rate of PdHx tetrapod nanocrystals into metallic Pd was faster than that of tetrahedral nanocrystals.MOST of China 2011CB932403 2009CB930703 NSFC 21131005 21021061 20925103 20973139 21133004 Fok Ying Tung Education Foundation 121011 Fundamental Research Funds for the Central Universitie

Synthesis of Ultrathin Nitrogen-Doped Graphitic Carbon Nanocages as Advanced Electrode Materials for Supercapacitor

E-mail Addresses: [email protected]; [email protected] of nitrogen-doped carbons with large surface area, high conductivity, and suitable pore size distribution is highly desirable for high-performance supercapacitor applications. Here, we report a novel protocol for template synthesis of ultrathin nitrogen-doped graphitic carbon nanocages (CNCs) derived from polyaniline (PAN!) and their excellent capacitive properties. The synthesis of CNCs involves one-pot hydrothermal synthesis of Mn3O4@PANI core-shell nanoparticles, carbonization to produce carbon coated MnO nanoparticles, and then removal of the MnO cores by acidic treatment. The CNCs prepared at an optimum carbonization temperature of 800 degrees C (CNCs-800) have regular frameworks, moderate graphitization, high specific surface area, good mesoporosity, and appropriate N doping. The CNCs-800 show high specific capacitance (248 F g(-1) at 1.0 A g(-1)), excellent rate capability (88% and 76% capacitance retention at 10 and 100 A g(-1), respectively), and outstanding cycling stability (similar to 95% capacitance retention after 5000 cycles) in 6 M KOH aqueous solution. The CNCs-800 can also exhibit great pseudocapacitance in 0.5 M H2SO4 aqueous solution besides the large electrochemical double-layer capacitance. The excellent capacitance performance coupled with the facile synthesis of ultrathin nitrogen-doped graphitic CNCs indicates their great application potential in supercapacitors.MOST of China 2011CB932403 National Natural Science Foundation of China 21075036 21175042 21131005 20925103 Program for Science and Technology Innovative Research Team in Higher Educational Institutions of Hunan Province Start-Up Fund for Young Teachers in Hunan Normal Universit

Facile synthesis of manganese-oxide-containing mesoporous nitrogen-doped carbon for efficient oxygen reduction

Developing low-cost non-precious metal catalysts for high-performance oxygen reduction reaction (ORR) is highly desirable. Here a facile, in situ template synthesis of a MnO-containing mesoporous nitrogen-doped carbon (m-N-C) nanocomposite and its high electrocatalytic activity for a four-electron ORR in alkaline solution are reported. The synthesis of the MnO-m-N-C nanocomposite involves one-pot hydrothermal synthesis of Mn3O 4@polyaniline core/shell nanoparticles from a mixture containing aniline, Mn(NO3)2, and KMnO4, followed by heat treatment to produce N-doped ultrathin graphitic carbon coated MnO hybrids and partial acid leaching of MnO. The as-prepared MnO-m-N-C composite catalyst exhibits high electrocatalytic activity and dominant four-electron oxygen reduction pathway in 0.1 M KOH aqueous solution due to the synergetic effect between MnO and m-N-C. The pristine MnO shows little electrocatalytic activity and m-N-C alone exhibits a dominant two-electron process for ORR. The MnO-m-N-C composite catalyst also exhibits superior stability and methanol tolerance to a commercial Pt/C catalyst, making the composite a promising cathode catalyst for alkaline methanol fuel cell applications. The synergetic effect between MnO and N-doped carbon described provides a new route to design advanced catalysts for energy conversion. Copyright 漏 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim

平面工艺空间带电粒子探测器的研制

描述了用平面工艺+离子注入技术制备新型空间带电粒子探测器的工艺技术及器件的特性。探测器的灵敏层厚度为100、300、450和1000μm,灵敏面积为(?)8和(?)12mm等不同规格。在全耗尽偏压下,得到典型的反向漏电流范围为0.57-10.11nA,典型的能量分辨率为0.69%-0.86%(对241Amα粒子)。在60℃高温下,器件的性能变化在空间应用的允许范围之内