自支撑氮掺杂石墨烯纸柔性电极的制备及其储锂性能的研究

以氧化石墨烯(GO)为原料,尿素为氮掺杂剂,采用固/气界面水热反应的方式,即在反应釜内将GO抽滤得到的氧化石墨烯纸(GOP)与尿素分解产生的氨蒸气相互作用,成功制备出自支撑氮掺杂石墨烯纸(NGP)。通过X射线衍射(XRD)、扫描电子显微镜(SEM)、拉曼光谱(RS)、X射线光电子能谱(XPS)和电化学测试对样品进行形貌结构及电化学性能的表征。测试结果表明:水热条件下尿素能有效地实现氧化石墨烯纸的氮掺杂,氮掺杂量为7.89%;氮掺杂石墨烯纸在100mA/g和500mA/g的电流密度下,充放电循环100周之后,放电比容量可分别保持在288mAh/g和190mAh/g。采用改进的固/气界面水热反应法制备的氮掺杂石墨烯纸较未掺杂石墨烯纸可逆比容量提高了近2.5倍,具有良好的循环稳定性,可为制备高性能的柔性锂离子电池负极材料提供新方法。     

Er对原位ZrB2/A356.2复合材料组织与性能的影响

采用原位合成法制备ZrB_2/A356.2复合材料,研究了引入ZrB_2对A356.2铸态微观组织的影响以及不同Er含量对复合材料铸态微观组织及力学性能的影响。结果表明,引入ZrB_2后α-Al晶粒和粗大共晶Si发生略微细化,添加Er后α-Al晶粒细化明显,并且Er对共晶Si有很好的变质效果,α-Al由粗大树枝晶变为蔷薇状、球状,共晶Si从粗大的针片状变为细小的短棒状、球状,有效提高了复合材料的力学性能。当Er添加量为0.10%(质量分数)时,其细化变质效果最为明显,复合材料力学性能提高最为显著。     

单晶PZT-CFO铁电-铁磁复合纳米纤维的制备与磁学性能研究

以不同锆掺杂量的前钙钛矿结构钛酸铅和铁酸钴为原料,采用原位固相烧结法合成了一系列单晶锆钛酸铅-铁酸钴(PZT-CFO)复合纳米纤维。X射线衍射、扫描电子显微镜和能谱分析结果表明,一维单晶PZT-CFO复合纳米纤维同时存在钙钛矿相的锆钛酸铅和尖晶石相的铁酸钴。高分辨透射电子显微镜研究证实锆钛酸铅和铁酸钴之间存在外延生长关系。采用振动样品磁强计对PZT-CFO复合纳米纤维的磁学性能进行测试,发现该复合纳米纤维具有明显的铁磁性能,其剩余磁化强度和矫顽力随着锆掺杂量的增加而增加。     

二次烧结气氛对La0.7Sr0.3MnO3氧还原催化活性的影响

采用溶胶一凝胶法结合二次高温烧结技术,制备了锰系钙钛矿催化剂.利用XRD和EDS对催化剂的物相与元素组成进行了分析,并利用电化学分析方法研究了催化剂的氧还原催化性能.XRD与EDS结果表明,N2气氛二次烧结不改变La0.7Sr0.3-MnO3物相组成,但NH3气氛二次烧结会造成Lao.7 Sr0.3MnO3分解.电化学结果表明,N2气氛二次烧结催化剂的氧还原催化活性高于NH3气氛二次烧结催化剂,其氧还原起始电势与极限电流分别为0.028 V(vs.Hg/HgO)和2.181 mA.cm-2(2 000 r/min).     

Diversity in Addressing Reaction Mechanisms of Nano‐Thermite Composites with a Layer by Layer Structure

The reaction mechanisms and microstructures of various layered nano‐thermite composites are investigated through characterization of their energetic properties. Migration of reactive components across the reaction zone is analyzed, which plays an important role in determining the process initiation, reaction propagation, and chemical stability at low temperatures. Distinct types of nanoparticles are deposited onto filter paper in a sequence, using the vacuum filtration method, which promotes intimate contact between neighboring reactive layers. Scanning Electron Microscopy (SEM) images demonstrate a well‐defined contact region between the two layers in the Al/CuO or Al/NiO composites. Differential Scanning Calorimetry (DSC) data shows that the thermite reaction occurs below the melting temperature of Al, resulting in rapid heat release, and improves reaction initiation. Elemental mapping results reveal the migration of Al, Ni/Cu, and oxygen before and after the thermite reaction, which is arranged during thermogravimetric analysis (TGA). This analysis indicates the dominant pathway of the thermite reaction in each composite, through either decomposition of the CuO nanoparticles in the Al/CuO composite or through direct migration of reactive components across the conducting surface within the Al/NiO composite.

     

Web‐Like Interconnected Carbon Networks from NaCl‐Assisted Pyrolysis of ZIF‐8 for Highly Efficient Oxygen Reduction Catalysis

The oxygen reduction reaction (ORR) is under intense research due to its significance in energy storage and conversion processes. Recent studies show that interconnected and hierarchically porous structures can further enhance ORR kinetics as well as catalyst durability, but their preparation can be quite time and/or chemical consuming. Here, a simple approach is reported to prepare such complex structures by pyrolyzing composites containing NaCl and ZIF‐8. The templating effect of molten NaCl connects ZIF‐8 particles into web‐like carbon networks. During ORR activity measurements, it achieves a 0.964 V onset potential and a 38 mV dec^?1 Tafel slope, which are comparable to those of the benchmark Pt/C (0.979 V and 40 mV dec^?1). Due to the metal‐free feature, this catalyst exhibits a 16 mV shift in half‐wave potential after a 10 000‐cycle durability test, which is only 60% of that of Pt/C. The catalyst is also tested in Zn–air batteries and the assemblies are able to work at above 1.2 V for 140 h, which triples the life held by those with Pt/C. This study demonstrates a facile strategy to prepare metal‐free ORR catalysts with interconnectivity and hierarchical porosity, and proves their great potentials in ORR catalysis and Zn–air batteries.     

Molybdenum Carbide‐Decorated Metallic Cobalt@Nitrogen‐Doped Carbon Polyhedrons for Enhanced Electrocatalytic Hydrogen Evolution

Electrocatalytic hydrogen evolution reaction (HER) based on water splitting holds great promise for clean energy technologies, in which the key issue is exploring cost‐effective materials to replace noble metal catalysts. Here, a sequential chemical etching and pyrolysis strategy are developed to prepare molybdenum carbide‐decorated metallic cobalt@nitrogen‐doped porous carbon polyhedrons (denoted as Mo/Co@N–C) hybrids for enhanced electrocatalytic hydrogen evolution. The obtained metallic Co nanoparticles are coated by N‐doped carbon thin layers while the formed molybdenum carbide nanoparticles are well‐dispersed in the whole Co@N–C frames. Benefiting from the additionally implanted molybdenum carbide active sites, the HER performance of Mo/Co@N–C hybrids is significantly promoted compared with the single Co@N–C that is derived from the pristine ZIF‐67 both in alkaline and acidic media. As a result, the as‐synthesized Mo/Co@N–C hybrids exhibit superior HER electrocatalytic activity, and only very low overpotentials of 157 and 187 mV are needed at 10 mA cm^?2 in 1 m KOH and 0.5 m H₂SO₄, respectively, opening a door for rational design and fabrication of novel low‐cost electrocatalysts with hierarchical structures toward electrochemical energy storage and conversion.     

Active Sites Engineering toward Superior Carbon‐Based Oxygen Reduction Catalysts via Confinement Pyrolysis

Developing efficient and low‐cost defective carbon‐based catalysts for the oxygen reduction reaction (ORR) is essential to metal–air batteries and fuel cells. Active sites engineering toward these catalysts is highly desirable but challenging to realize boosted catalytic performance. Herein, a sandwich‐like confinement route to achieve the controllable regulation of active sites for carbon‐based catalysts is reported. In particular, three distinct catalysts including metal‐free N‐doped carbon (NC), single Co atoms dispersed NC (Co–N–C), and Co nanoparticles‐contained Co–N–C (Co/Co–N–C) are controllably realized and clearly identified by synchrotron radiation‐based X‐ray spectroscopy. Electrochemical measurements suggest that the Co/Co–N–C catalyst delivers optimized ORR performance due to the rich Co–N_x active sites and their synergistic effect with metallic Co nanoparticles. This work provides deep insight for rationally designing efficient ORR catalyst based on active sites engineering.     

Revealing the Role of Electrocatalyst Crystal Structure on Oxygen Evolution Reaction with Nickel as an Example

Establishing a correlation between the crystal structure and electrocatalytic activity is crucial to the rational design of high performance electrocatalysts. In this work, taking the widely investigated nickel (Ni) based nonprecious oxygen evolution reaction (OER) catalyst as an example, for the first time, it is reported that the crystal structure plays a critical role in determining the OER performance. Similar‐sized nickel nanoparticles but in different hexagonal close‐packed phase and face‐centered cubic phase coated with N‐doped carbon shells, noted as hcp‐Ni@NC and fcc‐Ni@NC, are successfully prepared, respectively, in which the N‐coated carbon shell structures were also similar. Surprisingly, a dramatically enhanced OER performance of hcp‐Ni@NC in comparison with fcc‐Ni@NC is observed. The hcp‐Ni@NC only requires 305 mV overpotential to achieve the current density of 10 mA cm^?2, which is 55 mV lower than that of fcc‐Ni@NC, which can be ascribed to the influence of nickel crystal phase on the electron structure of N‐doped carbon shell. This finding will bring new thinking toward the rational design of high performance non‐noble metal electrocatalysts.     

Controlling Interactions of Cyclic Oligosaccharides with Hetero‐Oligomeric Nanopores: Kinetics of Binding and Release at the Single‐Molecule Level

Controlling the molecular interactions through protein nanopores is crucial for effectively detecting single molecules. Here, the development of a hetero‐oligomeric nanopore derived from Nocardia farcinica porin AB (NfpAB) is discussed for single‐molecule sensing of biopolymers. Using single‐channel recording, the interaction of cyclic oligosaccharides such as cationic cyclodextrins (CDs) of different symmetries and charges with NfpAB is measured. Studies of the transport kinetics of CDs reveal asymmetric geometry and charge distribution of NfpAB. The applied potential promotes the attachment of the cationic CDs to the negatively charged pore surface due to electrostatic interaction. Further, the attached CDs are released from the pore by reversing the applied potential in time‐resolved blockages. Release of CDs from the pore depends on its charge, size, and magnitude of the applied potential. The kinetics of CD attachment and release is controlled by fine‐tuning the applied potential demonstrating the successful molecular transport across these nanopores. It is suggested that such controlled molecular interactions with protein nanopores using organic templates can be useful for several applications in nanopore technology and single‐molecule chemistry.