CoMn@NC催化5-羟甲基糠醛常压氧化为2, 5-呋喃二甲酸二甲酯

Dimethyl furan-2, 5-dicarboxylate (DMFDCA) is a valuable biomass-derived chemical that is an ideal alternative to fossil-derived terephthalic acid as a monomer for polymers. The one-step oxidation of 5-hydroxymethylfurfural (HMF) to DMFDCA is of practical significance. It not only shortens the reaction pathway but also avoids the separation process of intermediates; thus, reducing cost. In this work, non-noble bimetallic catalysts supported on N-doped porous carbon (CoMn@NC) were synthesized via a one-step co-pyrolysis procedure using different pyrolysis temperatures and proportions of metal precursors and additives. We employed the prepared CoMn@NC catalysts in the aerobic oxidation of HMF under mild reaction conditions to obtain DMFDCA. High-yield DMFDCA was obtained by screening the prepared catalysts and optimizing the reaction conditions, including the strength and amount of the base, as well as the reaction temperature. The optimized yield of DMFDCA was 85% over the Co₃Mn₂@NC-800 catalyst after 12 h at 50 ℃ using ambient-pressure oxygen. The physicochemical properties of the catalysts were determined using a variety of characterization techniques, the factors affecting the performance of each catalyst were investigated, and the relationship between the physicochemical properties and performance of the prepared catalysts was elucidated. A porous structure with a high surface area had a positive effect on mass transfer efficiency. Cobalt nanoparticles (NPs) and atomically dispersed Mn were coordinated to N-doped carbon to form M―N_x (where M = Co or Mn). Based on the Mott-Schottky effect, there was significant electron transfer between each metal and the N-doped carbon, additionally, the metal NPs supplied electrons to the carbon atoms. The electron-deficient metal site in the pyridinic N-rich carbon was beneficial for the activation of HMF and oxygen. The activation of oxygen produced reactive oxygen species (such as superoxide radical anions) to ensure high selectivity to DMFDCA through dehydrogenative oxidation of the hemiacetal intermediate and hydroxymethyl group of 5-hydroxymethyl-2-methyl-furoate. The existence of disordered and defective carbons increased the number of active sites. Subsequently, we performed a series of control experiments. Based on our current experimental results and previous studies, we propose a simple mechanism for the aerobic oxidation of HMF to DMFDCA. The catalyst was stable, its performance decreased slightly after two cycles, and it was tolerant to SCN⁻ ions and resistant against N or S poisoning. Furthermore, the use of this catalytic system can be expanded to various substituted aromatic alcohols, such as benzyl alcohols with different substituents, furfuryl alcohol, and heterocyclic alcohols. Simultaneously, the product type was further extended from methyl esters to ethyl esters with a high yield when the substrate reacted with ethanol. In conclusion, this catalytic system can be applied in the production of carboxylic esters for polymers.     

硼、氮共掺杂多孔碳的制备及其超电容性能

分别以含氮菲咯啉、四硼酸钾和醋酸锌为碳源、活化剂和模板,制备了B、N共掺杂多孔碳(BN-PC),并探究模板质量对BN-PC结构和储电性能的影响。当醋酸锌质量为5 g时,所得BN-PC₅中B、N杂原子含量分别为20.21%、18.29%。电化学测试结果表明,以6 mol·L^-1KOH为电解液,BN-PC₅电极展现出高的比电容(在0.05 A·g^-1电流密度下为255 F·g^-1)、优异的倍率性能(在20 A·g^-1电流密度下为188 F·g^-1)和卓越的循环稳定性(在5 A·g^-1的电流密度下循环10 000次比电容保持率为97%)。以3mol·L^-1ZnSO₄为电解液,在平均功率密度为56 W·kg^-1时,BN-PC₅电容器的能量密度可达27 Wh·kg^-1。     

硼、磷共掺杂铁钴双金属材料的制备及其电催化析氧性能

采用一步水热法合成了硼、磷共掺杂铁钴材料(Fe-Co-B-P)。借助扫描电子显微镜(SEM)、X射线衍射(XRD)、X射线光电子能谱(XPS)、傅里叶变换红外光谱(FT-IR)等技术对所合成材料的形貌、结构和组成进行表征。利用线性扫描伏安(LSV)、循环伏安(CV)、电化学阻抗谱(EIS)等技术研究材料电化学析氧反应(OER)性能。结果表明,Fe-Co-B-P表面疏松且粗糙,颗粒间有许多空隙。在电流密度为10和100 mA·cm^-2时,其过电势分别为278和309 mV,Tafel斜率为24 mV·dec^-1,说明该材料具有较优的电催化析氧性能。其在连续进行10 h的计时电位测试过程中,电势基本保持在1.55 V(vs RHE),表明该催化剂具有较好的电化学稳定性。这是由于铁钴双金属与硼、磷非金属之间的协同作用促进了电子的传递。     

初始微观结构缺陷和断裂的温度依赖及相关性

纳米线(NW)结构内的微观结构缺陷对NW的机械性能存在一定的影响。NW断裂位置的预测关系着纳米器件应用的寿命,进而引起了人们的广泛关注。在本工作中,基于统计分析,分别研究了单晶铜纳米线(Cu NW)拉伸过程中出现的断裂位置以及在应力屈服点处产生的初始微观结构缺陷(初始缺陷)的位置对温度的依赖性,进一步探究了两者之间的联系。利用分子动力学(MD)模拟了单晶Cu NW在20~300 K的温度范围内的拉伸状态,共包含6个体系,各温度体系包含300个独立的样本。基于机器学习,采用density-based spatial clustering of applications with noise (DBSCAN)算法,将hexagonal close-packed (hcp)原子划分为各个初始缺陷以进一步确定其位置。统计结果显示,当温度低于50 K时,初始缺陷的位置集中在NW的两端。随着模拟温度的上升,MD模拟结果展现了单晶Cu NW的拉伸过程中的杨氏模量、平均屈服应力、平均势能等机械性能对温度的依赖性。温度的升高进一步促使了更多初始缺陷的产生,并使得初始缺陷的位置由统计分布的两端向中间平均化。与初始缺陷相比,各温度下的断裂位置集中在两端。统计结果表明,模拟的温度范围对NW的断裂位置无明显影响,但对初始缺陷的产生具有明显影响。当温度低于100 K时,初始缺陷的位置分布与断裂位置分布呈现了一致性。由于两者具有不同的温度依赖,其差异随着温度的上升逐渐显现。对不同温度下的微观结构形变行为观察发现,断裂失效明显受到NW两端的表面效应和阻挡效应的影响。最终的断裂位置受塑性形变中后期的影响,与应力屈服区产生的初始缺陷无直接联系。     

氟化氢溶液无电沉积法制备W掺杂Ag树枝晶

应用无电沉积在氟化氢溶液制备W掺杂Ag树枝晶,样品由XPS,XRD,SEM和TEM表征,结果表明在Ag-W二元体系中,Ag的生长起主导作用,不受钨酸根离子而改变。提出W元素的掺杂方式,即W元素的掺杂是在银的沉积过程中通过化学吸附—钨酸根二聚体的氧原子与银原子的化学作用力而实现的。循环伏安法用于检测银氧间的化学键能的强弱。     

Mg^2＋掺杂对锂离子正极材料Li3V2（PO4）3的影响

随着市场对锂离子电池(LIB)需求的日趋增长,对电极活性物质的要求也在朝着高能量密度、低成本、安全稳定、环境友好的方向努力,其中正极材料相对负极材料的发展较为缓慢,成为制约LIB发展的瓶颈。NASICON结构的Li3V2(PO4)3属于单斜晶系,相对金属锂具有很高的电势,理论容量高达19     

纯与掺杂CeO2的氧化还原性质及其催化领域的应用

概述了纯与掺杂CeO2氧化还原性质的研究状况及CeO2单独/主成分使用方式在催化领域中的应用.由于CeO2具有优异的储放氧性能,以及吸附气体和反应中间物能与几个Ce3 同时作用,其在氧化还原、合成气生产、有机合成和有机污染物降解等反应过程中呈现出良好的催化性能,而通过恰当的掺杂往往能使之得到进一步提高.最后,结合现状对其未来研究方向进行了展望.     

B离子掺杂TiO2催化剂(TiO2－xBx)光催化活性的研究

采用溶胶-凝胶法制备出纳米TiO₂和TiO_2－xB_x催化剂. 光催化实验证明, TiO_2－xB_x催化剂的紫外、可见光催化活性均高于TiO₂. XRD, XPS和Raman结果表明, B离子是以取代式掺杂占据了TiO₂的O^2－的晶格位置. UV-Vis和PL谱的结果表明, B离子的2p轨道与O的2p轨道形成混合价带, 产生可见光响应, B离子的掺入有效地阻止了光生载流子的复合, 促进了其分离, 是TiO_2－xB_x催化剂紫外、可见光催化活性提高的主要原因.     

镧掺杂锶铁氧体-聚吡咯复合物的制备及磁性研究

用溶胶-凝胶法和溶液原位合成法分别制备镧掺杂锶铁氧体(Sr1－xLaxFe11.5Ni0.5O19, x＝0.0, 0.1, 0.2, 0.3, 0.4)粉末及其吡咯相对质量分数为60%和80%的聚吡咯-铁氧体复合物微粒PPY (Polypyrrole)/Sr0.8La0.2Fe11.5Ni0.5O19. 借助X射线衍射(XRD)、透射电子显微镜(TEM)、扫描电子显微镜(SEM)、红外光谱(FTIR)和振动样品磁强计(VSM)等分析手段表征了铁氧体粉末和复合物微粒的结构、形貌和磁性能. 结果表明, 包覆的聚吡咯外层对复合物微粒的形貌和磁性有一定的影响. 在外加磁场作用下, 复合物的饱和磁化强度MS随吡咯含量的增加而减小, 当吡咯含量等于0%, 60%和80%时, 对应的MS分别为59.4, 18.7和10.3 emu/g.     

纳米ZnO/聚醋酸乙烯酯复合薄膜的光催化性能研究

采用溶胶-凝胶和浸渍-提拉而后煅烧的方法得到了在可见光作用下具有光催化性能的纳米ZnO/聚醋酸乙烯酯(PVAc)复合薄膜.通过正交设计实验,研究了PVAc的浓度、煅烧温度、煅烧时间、复合薄膜层数和附加ZnO膜层数等工艺因素对光催化性能的影响,并通过SEM,XRD和FT-IR对其进行了分析与表征.在室内普通照明用白炽灯作用下,以甲基橙溶液为催化对象,PVAc含量10%的、在250℃煅烧30min所得到的纳米ZnO/PVAe复合薄膜的光催化性能的实验结果表明,复合薄膜对甲基橙降解率达60%,而使用250℃煅烧30min所得到的纳米ZnO 4层薄膜或PVAc 4层薄膜催化的甲基橙溶液的浓度变化很小.