Rare earth metal based DES assisted the VPO synthesis for n-butane selective oxidation toward maleic anhydride

Deep eutectic solvents(DESs) are now considered a new class of ionic liquid analogs that have been generously used in various fields.Herein, vanadium phosphorus oxide(VPO) catalysts are synthesized in combination with a deep eutectic solvent containing rare earth metal(rE-DES), and their catalytic performance in n-butane selective oxidation to produce maleic anhydride(MA) is evaluated. The rE-DES is produced from the interaction of choline chloride(ChCl) and rare earth metal salts(Cerium, Europium, Lanthanum, and Samarium metal salt)(ChCl:rE = 1:0.5–1:3) under mild conditions. It was found that DESs served as structural modifiers and electronic promoters during VPO synthesis. It regulated the chemical state of the catalyst surface, such as the vanadium valence state, acid-base properties, and ratios of V^(4+)/V^(5+),Lat–O/Sur–O and P/V. Various characterization techniques, such as FT-IR, DSC, XRD, SEM, EDS, TEM, Raman, TGA, NH3-TPD, and XPS,were used to examine its physical and chemical characteristics. These characteristics were correlated with the catalytic performance. The VPO catalyst modified by rE-DES showed a significant enhancement of n-butane conversion and MA selectivity while suppressing the selectivity of CO and CO_(2)as well as the CO/CO_(2)ratio compared to the unpromoted VPO catalyst. Especially for Ce-DES-VPO, it increased the n-butane conversion and MA mass yield up to approximately 11% and 10%, respectively. In addition, we evaluated the catalytic performance under different activation atmospheres.

Progress of vanadium phosphorous oxide catalyst for n-butane selective oxidation

The utilization of lighter alkanes into useful chemical products is essential for modern chemistry and reducing the CO_(2)emission.Particularly,n-butane has gained special attention across the globe due to the abundant production of maleic anhydride(MA).Vanadium phosphorous oxide(VPO)is the most effective catalyst for selective oxidation of n-butane to MA so far.Interestingly,the VPO complex exists in more or less fifteen different structures,each one having distinct phase composition and exclusive surface morphology and physiochemical properties such as valence state,lattice oxygen,acidity etc.,which relies on precursor preparation method and the activation conditions of catalysts.The catalytic performance of VPO catalyst is improved by adding different promoters or co-catalyst such as various metals dopants,or either introducing template or structural-directing agents.Meanwhile,new preparation strategies such as electrospinning,ball milling,hydrothermal,barothermal,ultrasound,microwave irradiation,calcination,sol-gel method and solvothermal synthesis are also employed for introducing improvement in catalytic performance.Research in above-mentioned different aspects will be ascribed in current review in addition to summarizing overall catalysis activity and final yield.To analyze the performance of the catalytic precursor,the reaction mechanism and reaction kinetics both are discussed in this review to help clarify the key issues such as strong exothermic reaction,phosphorus supplement,water supplement,deactivation,and air/n-butane pretreatment etc.related to the various industrial applications of VPO.

Screening of Drought Resistance Identification Indexes for Rice(Oryza sativa L.) Cultivars in Ningxia

The morphological characters, physiological characters, yield traits and yield per plant of total 49 rice cultivars from Ningxia were investigated under conditions of water stress and non-water stress so as to determine the relationship between each trait and yield per plant under water stress and the relationship between each relative character and drought resistance coefficient under water stress and non-water stress. The correlation, grey correlation, stepwise regression and path analyses showed that the tiller number per plant, plant height, grain density, effective panicle number per plant and grain number per panicle, total 5 traits, were significantly correlated with the drought resistance of rice, and they could be used to identify the drought resistance of rice in Ningxia. In addition, the drought resistance of rice was graded qualitatively according to the subordinate function value of corresponding drought resistance coefficient. The results showed that among the 49 rice cultivars from Ningxia,6 rice cultivars were highly drought resistant, and 9 rice cultivars were moderately drought resistant, suggesting that the evaluation method was feasible and effective.

碱土金属醇类低共熔溶剂强化钒磷氧催化剂的制备及催化性能研究

钒磷氧(VPO)催化剂是目前实现正丁烷选择性氧化的唯一工业催化剂。利用金属助剂掺杂以及有机助剂强化是提高VPO催化剂性能的有效手段。本工作通过加入氯化镁醇类金属低共熔溶剂,实现了有机-金属助剂同时对VPO催化剂性能的调控。利用扫描电子显微镜(SEM)、BET全自动比表面与孔隙度分析仪(BET)、X射线衍射仪(XRD)和X射线光电子能谱仪(XPS)等表征手段,深入探讨了合成过程中加入不同氢键供体乙二醇(EG)、1-4丁二醇(BDO)和甘油(GL)的低共熔溶剂对VPO催化剂微观形貌、比表面积、物相、表面性质和晶相转变温度的影响,同时利用固定床反应器对VPO催化剂催化正丁烷氧化制备顺酐的性能进行了评价。结果表明,氯化镁乙二醇低共熔溶剂调控制备的VPO催化剂具有分散性良好、比表面积大、活性面(020)的数量多、表面P原子富集和表面V平均价态低等特点,在丁烷氧化选择性制顺酐反应中表现出了良好的催化性能,为VPO催化剂的制备提供了新思路。

Development of a correlation equation between the diesterification of maleic anhydride and the acidic ionic liquids nature

The sustainable synthesis of dimethyl maleate via diesterification through the utilization of ionic liquid(IL)is of great importance.However,the relationship between the ILs nature and the reactivity of diesterification is still unclear.Herein,a series of ILs with different structures were selected for the comprehensive investigation of diesterification.The acidity(H_(0))and Kamlet-Taft solvent parameters(hydrogen bond donor ability(α),hydrogen bond acceptor ability(β),and polarizability(π^(*)))of ILs were measured by UV–Visible spectroscopy,and the effects of them on the diesterification of maleic anhydride were also studied in detail.The results indicated that not only H0of the IL-based catalysis system,but also itsα,β,andπ^(*)influenced the reaction activity of diesterification.Furthermore,a quantifiable correlation was fitted between the natural logarithm of the rate constant and multiple parameters of ILs,indicating that the diesterification rate had a positive correlation with the H0,α,andπ^(*),and inverse correlation with theβof the IL.A plausible synergetic reaction mechanism for the excellent performance of[(HSO_(3))PMim][HSO_(4)]has been proposed.Overall,this work thoroughly explored the relationship between the nature of ILs on diesterification in-depth,which will reveal the nature of diesterification in detail.

Fabrication of Regular Hierarchical Structures with Superhydrophobic and High Adhesion Performances on a 304 Stainless Steel Surface via Picosecond Laser

Hierarchical structures significantly influence the development of metal surface wettability.In this study,three kinds of hierarchical structures fbimed by the superimposition of different nanoscale(quasi-)periodic structures on micro-column arrays were fabricated on 304 stainless steel surfaces via picosecond laser irradiation.Scanning Electron Microscope(SEM)and Confocal Laser Scanning Microscope(CLSM)were used to characterize the created hierarchical structures.An optical contact angle meter was used to analyse the wetting performances.The results show that the surfaces of these fabricated samples have superhydrophobic properties and strong adhesion per formances,which can be attributed to the formation of hierarchical structure that causes a reduction in the liquid-solid contact area and the change in the direction of surfece tension.By controlling the dimensionof the nanotextures on the micro-column arrays,the hydrophobic property of 304 stainless steel surfaces can be greatly improved.