电解质的非均相化现象对钨离子交换的影响

研究了电解质非均相化现象对钨离子交换的影响。研究表明:WO42-和Cl-的非均相化差异导致WO42-正向吸附的工作交换容量降低,逆向吸附的工作交换容量提高;提高交前液WO42-浓度,增大树脂层高度,降低离子交换线速度可扩大正逆向吸附交换容量的差异。正向解吸速度降低可提高解吸液浓度、减少解吸剂的用量。

非均相催化臭氧化污水处理技术研究进展

非均相催化臭氧化技术因具有反应快、无二次污染、处理效率高等优点而得到快速发展。通过介绍金属氧化物催化剂、金属羟基氧化物催化剂以及负载型催化剂,总结了近几年国内外非均相催化臭氧化催化剂的处理效果、催化机理等,分析了该技术的优势、存在的问题,指出了未来的发展方向。

非均相催化臭氧化深度处理钻井废水的效能研究

采用单独臭氧氧化、MnO2吸附和O3/MnO2催化氧化3种体系对经过混凝处理后的钻井废水进行深度处理,重点研究了O3/MnO2催化氧化体系去除钻井废水中有机物(以COD计)的效能。结果表明:相比单独臭氧氧化和MnO2吸附体系,O3/MnO2催化氧化体系能显著提高COD和TOC的去除率;COD去除率随着臭氧投加量和催化剂投加量的增加、pH的升高和反应时间的增加而增大;在臭氧投加量为80 mg/L、pH为11.5、催化剂投加量为20 g/L、反应时间为40 min的最佳工艺条件下,COD和TOC的去除率分别达到87.51%、83.18%,COD从686.28 mg/L降至85.72mg/L,出水达到《污水综合排放标准》(GB 8978—1996)的一级标准要求。

非均相催化臭氧化处理钻井废水的研究

以油田钻井废水为处理对象,采用基于臭氧的非均相催化氧化处理工艺,负载了MnO_(2)催化剂强化臭氧处理效果,实验对比分析单独臭氧化和非均相催化臭氧化的处理效果差异,确定最佳工艺参数条件。X射线衍射分析表明,过量浸渍法制备的催化剂中含有大量活性组分MnO_(2),使非均相催化臭氧化去除钻井废水COD的效率提高了45.8%。经工艺优化后,确定非均相催化臭氧化处理钻井废水最佳条件为:催化剂加量50 mg/L、反应pH值为11、反应温度20℃、臭氧浓度85 mg/L、处理时间50 min,此时废水COD最大去除率为83.1%。通过5次重复实验验证,催化剂和系统稳定性几乎不受影响,出水均达到GB 8978—1996《污水综合排放标准》一级标准。

水中PPCPs的暴露及其非均相催化臭氧化控制研究进展

近年,药品及个人护理品(PPCPs)的产量和用量不断提升,导致废水中PPCPs的检出浓度和检出频率递增.在环境中多数PPCPs不易分解,可持续存在并保持毒性,对水生态造成慢性影响.大量研究证明,污水二级处理很难实现PPCPs的稳定去除,需要依托臭氧等深度处理工艺.臭氧分子仅对某些特定结构的PPCPs活性高,且氧化速率易受pH值、PPCPs基团电子特性等影响.催化臭氧化技术因可以大量产生具有强氧化性且对PPCPs结构无选择性的·OH而受到关注.笔者综述了PPCPs水污染现状,对比分析了臭氧工艺、催化臭氧化工艺对水中PPCPs的控制效果,总结了非均相催化臭氧化工艺在提高PPCPs矿化效果与工艺适用性等方面的优势,并对非均相催化臭氧化技术的研究方向进行了展望.

纳米流体沸腾核化的热力学探讨

基于经典的核化理论,将纳米流体看成是一个均匀的体系,不考虑颗粒的团聚及其在壁面处的富集和沉积,仅考虑体相纳米颗粒的影响。将纳米颗粒类比为大分子溶质,基液类比为溶剂,则纳米流体便可看作是浓度极稀的溶液,借用溶液热力学的相关理论,并假设气液界面处的颗粒是单层嵌入的方式且排布均匀,分别建立了纳米流体的均相和非均相核化模型,分析探讨颗粒对核化的影响。结果表明,纳米颗粒在界面处的吸附可减小核化的平衡胚泡半径,降低沸腾核化势垒,有利于核化的发生。

Heterogeneous Uptake of Hydrogen Peroxide on Mineral Oxides

The interaction of mineral oxides （α-A12O3, MgO, Fe2O3, and SiO2） with hydrogen peroxide was investigated using the Knudsen cell reactor. The initial reactive uptake coefficients for tile commercially available powders are measured as （1.00±0.11）×10-4 for α-A1203, （1.66±0.23）×10-4 for MgO, （9.70±1.95）×10-5 for Fe203, and （5.22±0.9）×10-5 for SiO2. These metal oxide powders exhibit some catalytic behavior toward the decomposition of hydrogen peroxide excluding SiO2. H2O2 can be destroyed on Fe2O3 surface and O2 is formed. The experimental results suggest that the heterogeneous loss on mineral surface can represent an important sink of hydrogen peroxide.

Time-temperature-property curves for quench sensitivity of 6063 aluminum alloy

The quench sensitivity of 6063 alloy was investigated via constructing time-temperature-property（TTP） curves by interrupted quenching technique and transmission electron microscopy（TEM） analysis.The results show that the quench sensitivity of 6063 alloy is lower than that of 6061 or 6082 alloy,and the critical temperature ranges from 300 to 410℃ with the nose temperature of about 360℃.From TEM analysis,heterogeneous precipitate β-Mg2Si is prior to nucleate on the（AlxFeySiz） dispersoids in the critical temperature range,and grows up most rapidly at the nose temperature of 360℃.The heterogeneous precipitation leads to a low concentration of solute,which consequently reduces the amount of the strengthening phase β＇＇ after aging.In the large-scale industrial production of 6063 alloy,the cooling rate during quenching should be enhanced as high as possible in the quenching sensitive temperature range（410-300℃） to suppress the heterogeneous precipitation to get optimal mechanical properties,and it should be slowed down properly from the solution temperature to 410℃ and below 300℃ to reduce the residual stress.

Iron-glutamate-silicotungstate ternary complex as highly active heterogeneous Fenton-like catalyst for 4-chlorophenol degradation

A novel iron-glutamate-silicotungstate ternary complex（FeШGluS iW） was synthesized from ferric chloride（FeI II）,glutamic acid（Glu）,and silicotungstic acid（SiW）,and used as a heterogeneous Fenton-like catalyst for 4-chlorophenol（4-CP） degradation at neutral pH value. The prepared FeШGluS iW was characterized using inductively coupled plasma atomic emission spectroscopy,thermogravimetry,Fourier-transform infrared spectroscopy,ultraviolet-visible diffuse reflectance spectroscopy,X-ray diffraction,and field-emission scanning electron microscopy. The results showed that FeШGluS iW has the formula [Fe（C5H8NO4）（H2O）]2SiW 12O40？13H2O,with glutamate moiety and Keggin-structured SiW 12O404- heteropolyanion. The catalyst showed high catalytic activity in 4-CP degradation in the dark and under irradiation. Under the conditions of 4-CP 100 mg/L,FeШGluS iW 1.0 g/L,H2O2 20 mmol/L,and pH = 6.5,4-CP was completely decomposed in 40 min in the dark and in 15 min under irradiation. When the reaction time was prolonged to 2 h,the corresponding total organic carbon removals under dark and irradiated conditions were ca. 27% and 72%,respectively. The high catalytic activity of FeI IIGluS iW is resulted from hydrogen bonding of H2O2 on the FeI IIGluS iW surface. The enhanced degradation of 4-CP under irradiation arises from simultaneous oxidation of 4-CP through Fenton-like and photocatalytic processes respectively catalyzed by ferric iron and the SiW 12O404- hetropolyanion in FeШGluS iW.

State-of-the-art catalysts for direct dehydrogenation of propane to propylene

With growing demand for propylene and increasing production of propane from shale gas,the technologies of propylene production,including direct dehydrogenation and oxidative dehydrogenation of propane,have drawn great attention in recent years.In particular,direct dehydrogenation of propane to propylene is regarded as one of the most promising methods of propylene production because it is an on-purpose technique that exclusively yields propylene instead of a mixture of products.In this critical review,we provide the current investigations on the heterogeneous catalysts(such as Pt,CrOx,VOx,GaOx-based catalysts,and nanocarbons)used in the direct dehydrogenation of propane to propylene.A detailed comparison and discussion of the active sites,catalytic mechanisms,influencing factors(such as the structures,dispersions,and reducibilities of the catalysts and promoters),and supports for different types of catalysts is presented.Furthermore,rational designs and preparation of high-performance catalysts for propane dehydrogenation are proposed and discussed.

Direct Synthesis of Diphenyl Carbonate with Heterogeneous Catalyst and Optimal Synthesis Conditions of the Support Prepared by Sol-gel Method

The support of catalyst for the direct synthesis of diphenyl carbonate （DPC） by heterogeneous catalytic reaction was prepared by the sol-gel method. Compared with activated charcoal, molecular sieve, porous ceramics, hopcalite, the support prepared by the sol-gel method has higher activity. The characterization of the support by X-ray diffraction （XRD） and transmission electron microscope （TEM） show that the mare crystal phase is Co2MnO4 and the average particle diameter is about 40 nm. The optimum conditions for synthesis of the support were determined by orthogonal experiments, which indicate that the proportion of Cu, Mn, and Co is the first important factor influencing the yield and selectivity of DPC. Temperature of calcination is the second one. The optimum conditions are： molar proportion of Cu, Mn, and Co being 1 ： 1 ： 1, temperature of calcination 700℃, drying at 100~C, temperature of water bath 85~C. The yield and selectivity of DPC in the process can reach 38% and 99% in the batch operation, respectively. The copper cobalt manganese mixed oxides chosen as the support contribute more to the high catalytic activity than the sol-gel method.

Efficient and stable Ru(Ⅲ)-choline chloride catalyst system with low Ru content for non-mercury acetylene hydrochlorination

Herein,we report an excellent,supported Ru(III)‐ChCl/AC catalyst with lower Ru content,where the ionic complex ChRuCl4 serves as the active component for acetylene hydrochlorination.The prepared heterogeneous Ru‐10%ChCl/AC catalyst shows excellent activity and long‐term stability.In this system,ChCl provides an environment for the ChRuCl4 to be stabilized as Ru(III),thus suppressing the reduction of the active species and the aggregation of ruthenium species during the reaction.The interaction between reactants and catalyst species was investigated by catalyst characterizations in combination with DFT calculations to disclose the effect of the ChRuCl4 complex and ChCl on the catalytic performance.This inexpensive,efficient,and long‐term catalyst is a competitive candidate for application in the hydrochlorination industry.

Study on Direct Synthesis of Diphenyl Carbonate with Heterogeneous Catalytic Reaction (V) Screening Catalysts and Optimizing Synthesis Conditions

Pd/LaxPbyMnOz, Pd/C, Pd/molecular sieve and Pd-heteropoly acid catalysts for direct synthesis of diphenyl carbonate (DPC) by heterogeneous catalytic reaction were compared and the results of DPC synthesis indicated that the catalyst Pd/LaxPbyMnOz had higher activity. The Pd/LaxPbyMnOz catalyst and the support was characterized by XRD, SEM and TEM, the main phase was Lao.szPbo.asMnOa and the average diameter could be about 25.4nm. The optimuna conditions for synthesis of DPC with Pd/LasPbyMnOz were determined by orthogonal experiments and the experimental results showed that reaction temperature was the first factor of effect on the selectivity and yield of DPC, and the concentration of O2 in gas phase also had significant effect on selectivity of DPC. The optimum reaction conditions were catalyst/phenol mass ratio l to 50, pressure 4.5MPa, volume concentration of O2 25%, reaction temperature 60℃ and reaction time 4 h. The maximum yield and average selectivity could reach 13% and 97% respectively in the batch operation.

Catalytic ozonation of phenol and oxalic acid with copper-loaded activated carbon

A novel heterogeneous catalytic ozonation process in water treatment was studied, with a copper-loaded activated carbon （Cu/AC） that was prepared by an incipient wetness impregnation method at low temperature and tested as a catalyst in the ozonation of phenol and oxalic acid. Cu/AC was characterized using XRD, BET and SEM techniques. Compared with ozonation alone, the presence of Cu/AC in the ozonation processes significantly improves the degradation of phenol or oxalic acid. With the introduction of the hydroxyl radical scavenger, i.e., turt-butanol alcohol （t-BuOH）, the degradation efficiency of both phenol and oxalic acid in the Cu/AC catalyzed ozonation process decreases by 22% at 30 min. This indicates that Cu/AC accelerates ozone decomposition into certain concentration of hydroxyl radicals. The amount of Cu（II ） produced during the reaction of Cu/AC-catalyzed ozonation of phenol or oxalic acid is very small, which shows that the two processes are both heterogeneous catalytic ozonation reactions.

Direct carbon dioxide hydrogenation to produce bulk chemicals and liquid fuels via heterogeneous catalysis

The hydrogenation of carbon dioxide(CO_(2))to produce chemicals and transportation liquid fuels in huge demand via heterogeneous thermochemical catalysis achieved using renewable energy has received increasing attention,and substantial advances have been made in this research field in recent years.In this study,we summarize our progress in the rational design and construction of highly efficient catalysts for CO_(2) hydrogenation to methanol,lower olefins,aromatics,and gasolineand jet fuel-range hydrocarbons.The structure‐performance relationship,nature of the active sites,and mechanism of the reactions occurring over these catalysts are explored by combining computational and experimental evidence.The results of this study will promote further fundamental studies and industrial applications of heterogeneous catalysts for CO_(2) hydrogenation to produce bulk chemicals and liquid fuels.

Optimization of a digested sludge-derived mesoporous material as an efficient and stable heterogeneous catalyst for the photo-Fenton reaction

The anaerobic digestion of sludge has recently received increased interest because of the potential to transform organic matter into methane‐rich biogas. However, digested sludge, the residue produced in that process, still contains high levels of heavy metals and other harmful substances that might make traditional disposal difficult. We have devised a facile method of converting digested sludge into a mesoporous material that acts as an effective and stable heterogeneous catalyst for the photo‐Fenton reaction. A comparison of the removal of rhodamine B under different conditions showed that FAS‐1‐350, which was synthesized by mixing the digested sludge with a 1 mol/L（NH4）2Fe（SO4）2 solution followed by calcination at 350 °C, exhibited the best catalytic activity owing to its faster reaction rate and lower degree of Fe leaching. The results indicate that Fe^（2＋）‐loaded catalysts have significant potential to act as stable and efficient heterogeneous promoters for the photo‐Fenton reaction, with better performance than Fe^3＋‐loaded catalysts because the Fe（II）/Fe（III）compounds formed in the calcination process are necessary to sustain the Fenton reaction. This protocol provides an alternative, environmentally friendly method of reusing digested sludge and demonstrates an easily synthesized mesoporous material that effectively degrades azo dyes.

Mn-corrolazine-based 2D-nanocatalytic material with single Mn atoms for catalytic oxidation of alkane to alcohol

Heterogenization of organic-macrocyclic metal catalysts is one of the simplest and most efficient methods for effective separation of products and cyclic application of a catalyst.By using an environmentally friendly Mn-corrolazine catalyst as the building unit,which can directly oxidize organic substrates under oxygen atmosphere and mild conditions,we theoretically constructed a novel two-dimensional(2D)Mn-corrolazine nanocatalytic material with high catalytic activity.In this material,each Mn atom maintains its electronic configuration in the monomer and can directly activate O2 as the single-atom catalyst(SAC)center to form a radical-like[Mn]-O-O under mild visible-light irradiation conditions.The newly generated[Mn]–O–O can efficiently and selectively oxidize C–H bonds to form alcohol species through H-abstraction and the rebound reaction.Moreover,the catalytic reaction is easily regulated by an external electric field along its intrinsic Mn–O–O reaction axis.The current study provides a theoretical foundation for further experimental studies and practical applications of the Mn-corrolazine-based SAC.

Catalytic ativities of single-atom catalysts for CO oxidation: Pt_1/FeO_x vs. Fe_1/FeO_x

An FeOx‐based Pt single‐atom catalyst(SAC),Pt1/FeOx,has stimulated significant recent interest owing to its extraordinary activity toward CO oxidation.The concept of SAC has also been successfully extended to other FeOx supported transition metal systems both experimentally and theoretically.However,the FeOx substrate itself(denoted by Fe1/FeOx following the same nomenclature of Pt1/FeOx)as a typical transition metal oxide possesses a very low catalytic activity toward CO oxidation,although it can be viewed as Fe1/FeOx SAC.Here,to understand the catalytic mechanism of FeOx‐based SACs for CO oxidation,we have performed density functional theory calculations on Pt1/FeOx and Fe1/FeOx for CO oxidation to address the differences between these two SACs in terms of the catalytic mechanism of CO oxidation and the chemical behavior of the catalysts.Our calculation results indicated that the catalytic cycle of Fe1/FeOx is much more difficult to accomplish than that of SAC Pt1/FeOx because of a high activation barrier(1.09eV)for regeneration of the oxygen vacancy formed when the second CO2molecule desorbs from the surface.Moreover,density of states and Bader charge analysis revealed differences in the catalytic performance for CO oxidation by the SACs Fe1/FeOx and Pt1/FeOx.This work provides insights into the fundamental interactions between the single‐atom Pt1and FeOx substrate,and the exceptional catalytic performance of this system for CO oxidation.

Quaternary-ammonium-immobilized polystyrenes as efficient and reusable heterogeneous catalysts for synthesis of cyclic carbonate:Effects of linking chains and pendent hydroxyl group

Spherical polystyrene‐supported ammonium salts containing different linking chains between the support and ammonium groups were prepared as efficient and easily reusable heterogeneous catalysts for the cycloadditions of CO2and epoxides.The effects of the length of the linking chains and a hydroxyl group pendent on the linking chain on the catalytic performance of ionic liquid immobilized catalysts and their mechanisms were studied through experiments and density functional theory calculations.It was found that,compared with a short linking chain,a long chain can make the halogen anion more negative and provide a larger contact area of the catalysts with the reactants,thus enhancing the reaction kinetics.The hydroxyl group can stretch the C-O bonds of the epoxides,promoting the reaction thermodynamics.As a result,for the cycloaddition of propylene oxide,the yield of propylene carbonate is much higher for the catalyst with a long linking chain(yield:91.4%)compared with the yield for that with a short chain(yield:70.9%),and is further increased in the presence of pendent hydroxyl groups(yield:98.5%).The catalyst also shows a high catalytic activity even at mild temperature and good reusability(yield:≥96%for10cycles),and the selectivity is always above99%.