非晶态有机锆聚合物制备及其光催化CO2合成甲醇

采用溶剂热法在增透的多孔玻璃表面制备负载非晶态有机锆聚合物,通过SEM、XRD、BET、FTIR、UV-Vis、ICP、有机元素分析、荧光光谱(PL)及紫外光电子能谱(UPS)等手段对样品进行了表征。结果表明,非晶态有机锆聚合物(2.64 eV)具有比NH_2-Ui O-66(Zr)(2.74 eV)更窄的带隙,复合速率较慢的光生电子-空穴对。在光催化反应器中放入2片负载非晶态有机锆的玻璃(总面积50.4 cm~2),在300 W的氙灯照射下催化还原CO_2合成甲醇,反应4 h后甲醇的产量为443.0μmol,转换频率(TOF)为8.69 h~(–1)。当0.1 g NH_2-UiO-66(Zr)为催化剂时,甲醇的产量为244.3μmol,TOF仅为0.17 h~(–1)。非晶态有机锆聚合物的光催化性能明显优于NH2-UiO-66(Zr)粉末,且循环稳定性良好。     

有机锆聚合物气凝胶的制备及光催化还原CO2

以2-氨基对苯二甲酸(NH2-BDC)为配体、四氯化锆为Zr4+源,采用溶胶-凝胶法制备了4种不同配体/金属离子物质的量比的气凝胶,并通过SEM、BET、FTIR、XPS、UV-Vis、荧光光谱等表征了材料的结构及光电性能.结果表明,这种气凝胶不仅具有大的比表面积与丰富的孔道结构,而且在氙灯照射下具有光电效应,可以在水中催化还原CO2生成甲醇.在300 W的氙灯照射下,研究了不同配体/金属离子物质的量比对光催化还原CO2的影响.结果表明,当气凝胶中n(NH2-BDC):n(Zr4+)的实际比例为1.10:1时,4 h光催化反应后甲醇产率为3.94 mmol/g-cat,催化转换频率(TOF)为2.29 h–1.相同催化反应条件下以NH2-UiO-66(Zr)为光催化剂,甲醇的产率为2.33 mmol/g-cat,TOF为1.80 h–1.此外,该气凝胶具有较好的光催化稳定性.     

微波法制备磷酸锆的研究

采用氧氯化锆为锆源、氟化铵为络合剂、磷酸为磷源,在低温（〈100℃）和常压条件下,微波辅助加热法在较短时间内制备得到规则的六角形片状结构Zr（HPO4）2·H2O（简写为α-ZrP）晶体。研究了不同反应物浓度下NH4F与ZrOCl2·8H2O摩尔比、磷酸与ZrOCl2·8H2 O摩尔比、反应时间、反应温度等因素对于合成磷酸锆晶体的影响。产物采用XRD、 SEM和FT-IR表征。以罗丹明B为降解对象,可见光下研究所制备磷酸锆的光催化性能。结果表明,当[ Zr^4＋]=0.02 mol/L, NH4 F/Zr=6和P/Zr=40,微波加热温度90℃,反应时间为30 min时制备的磷酸锆具有良好的光催化活性。     

金属有机骨架材料NH_2-UIO-66(Zr)及其后修饰材料的合成

以2-氨基对苯二甲酸为有机配体,无水四氯化锆为金属前驱体,DMF为溶剂,通过溶剂热法合成具有优良稳定性的氨基取代的金属-有机骨架材料NH_2-UIO-66(Zr)。通过XPS和SEM表征其构成和微观形貌,SEM图显示为不规则的颗粒状物质,孔径在2~9μm。进一步在NH_2-UIO-66(Zr)上负载了Pd纳米颗粒形成Pd@NH_2-UIO-66(Zr)材料,金属有机骨架材料结构特征均保留下来,在催化剂方面有很好的发展潜力。     

微波法制备磷酸锆的研究

采用氧氯化锆为锆源、氟化铵为络合剂、磷酸为磷源,在低温(<100℃)和常压条件下,微波辅助加热法在较短时间内制备得到规则的六角形片状结构Zr(HPO4)2·H2O(简写为α-ZrP)晶体。研究了不同反应物浓度下NH4F与ZrOCl2·8H2O摩尔比、磷酸与ZrOCl2·8H2O摩尔比、反应时间、反应温度等因素对于合成磷酸锆晶体的影响。产物采用XRD、SEM和FT-IR表征。以罗丹明B为降解对象,可见光下研究所制备磷酸锆的光催化性能。结果表明,当[Zr4+]=0.02mol/L,NH4F/Zr=6和P/Zr=40,微波加热温度90℃,反应时间为30min时制备的磷酸锆具有良好的光催化活性。     

Zr掺杂g-C3N4光催化降解有机污染物

以盐酸胍为前驱体，硝酸锆为锆源，通过热聚合法制备了Zr掺杂的Zr/g-C3N4光催化剂。运用XRD、SEM、UV-Vis DRS、PL、XPS、BET等手段对催化剂的结构、形貌、光学性能进行了表征分析。结果表明：Zr掺杂改性的Zr/g-C3N4光催化剂拓宽了可见光的吸收，增大了比表面积，且降低了光生电子-空穴的复合率，具有较好的光催化活性。可见光照射下，在60 min内，5Zr/g-C3N4对罗丹明B（RhB）的光催化降解率达99.29%，光催化降解过程符合一级动力学方程，其速率常数k= 0.08647 min-1，是纯g-C3N4的8.3倍。捕获剂实验发现降解RhB的主要活性物种为超氧自由基，并推测了可能的反应机理。     

BiVO4/rGO复合物的制备及其 光催化还原CO2研究

采用水热法制备了颗粒状单斜相钒酸铋（BiVO4）/还原氧化石墨烯（rGO）复合催化剂。采用傅里叶红外光谱、拉曼光谱、X射线衍射和紫外-可见漫反射光谱对合成的复合材料做了表征。采用透射电镜、扫描电镜和氮吸附脱附实验对复合材料的表面形貌和表面积做了分析测试。实验结果表明,BiVO4复合物能选择性将CO2还原成甲醇,石墨烯的引入能很好地改善BiVO4光催化还原CO2的性能。当石墨烯的加入量为3%（质量分数）时,在氙灯功率为600 W的条件下,光照6 h后,BiVO4/rGO复合材料光催化还原CO2生成的甲醇产量达到513.1 μmol/L,比相同形貌的纯BiVO4的甲醇产量高73.6%。     

新型苯加氢制环己烯Ru-B/ZnO-ZrO_2催化剂的制备与表征

制备了不同n（Zn）∶n（Zr）的双组分氧化物载体,并进行了各种表征。XRD、TEM结果表明ZnO-ZrO2为纳米级,N2吸附表明不同n（Zn）∶n（Zr）的载体具有相近的比表面积、孔体积和平均孔径等组织结构性质。采用化学还原法负载Ru活性组分,并对催化剂进行了XRD、DSC等表征,结果表明：Ru-B/ZnO-ZrO2催化剂中Ru-B为非晶态合金,ZrO2为四方型,Ru活性组分很好的分散于载体上。该催化剂在140℃、4 MPa氢气压力和0.2 mol/L ZnSO4溶液下进行苯加氢制环己烯反应时,环己烯最大收率可达43%。     

CuO/TiO2纳米纤维可见光催化CO2合成甲醇

以介孔SiO_2球为模板、TiCl4为前驱体,采用气相生长法制备了直径为8～10nm的TiO_2纳米纤维,然后采用浸渍法制备了具有异质结结构的CuO/TiO_2纳米纤维,在可见光照射下催化CO_2合成甲醇。通过SEM、TEM、XPS、UV-Vis、XRD、荧光光谱(PL)对催化剂进行了表征。结果表明:TiO_2纳米纤维较锐钛矿TiO_2纳米颗粒和商业TiO_2纳米颗粒(P25)荧光强度明显降低,光生电子-空穴对更加稳定。通过在TiO_2纳米纤维上负载CuO形成异质结结构后,进一步降低了催化剂的荧光强度,也增强了在可见光区的吸收。在300 W氙灯照射5 h进行光催化CO_2合成甲醇实验中,P25负载CuO后,催化合成甲醇产量为676μmol/g-cat,而负载了CuO的TiO_2纳米纤维,甲醇产量达1791μmol/g-cat,较CuO/P25提高了165%。     

新型Cu/ZrO2环己醇脱氢催化剂的制备

以硝酸铜、氧氯化锆为原料，配制成n(Zr)∶n(Cu)＝（1～4）∶1的溶液，以w（NaOH）＝15％溶液为沉淀剂，采用共沉淀法，制备出新型Cu/ZrO₂环己醇脱氢催化剂。通过正交试验选择出较优的催化剂制备条件为：n(Zr):n(Cu)=2∶1，锆盐初始浓度0.2 mol·L^－1，焙烧时间5 h，焙烧温度400 ℃，滴定终点pH值为12。考察了催化剂预处理、反应温度等对脱氢过程产物收率和选择性的影响。在优化条件下制得的催化剂用于环己醇脱氢时，环己酮产品收率达85%，选择性近100％。     

乙烯酮(双乙烯酮)下游产品废水的治理技术

乙烯酮(双乙烯酮)是十分重要的化工中间体,其下游产品较多。江苏某化工厂开发生产乙烯酮(双乙烯酮)下游产品三十多个,年生产规模三万多吨,是国内以乙烯酮(双乙烯酮)为中间体生产精细化学品的综合骨干企业。针对乙烯酮(双乙烯酮)下游产品废水特点,该厂结合企业实际,开展了产品优化,结构调整,清洁生产,资源循环利用,节水降耗等工作,从源头削减了污染物的生产。同时投资二千多万元新建预处理装置三套,6000m3/d废水生化处理装置一套,使全厂乙烯酮(双乙烯酮)下游产品的废水得到了有效的治理。     

几种乙炔加压设备性能的比较

阐述并比较了几种加压设备在乙炔加压清净过程中的性能和特点。     

三种煤样燃烧热的测定

本文通过三个厂家提供的三种煤样燃烧热的测定,由测定结果综合得出3号煤样燃烧最完全、燃烧热也最大,是三个煤样中最好的一种。     

Semi-empirical equation of state of metals. Equation of state of aluminum

A semi-empirical equation of state for metals is described. Its capabilities are demonstrated by the example of the equation of state for aluminum. New experimental data are presented on the location of the isentrope of aluminum for unloading from the state at p = 229.71 GPa on the shock adiabat to an aerogel (SiO₂) of density 0.08 g/cm³. __________ Translated from Fizika Goreniya i Vzryva, Vol. 44, No. 2, pp. 61–75, March–April, 2008.     

小议汽车涂装工艺设计对涂装成本的影响

论述了涂装工艺设计对涂装设备投资、涂装生产成本的影响。     

水泥水化热测定方法综述

水泥水化热是中、低热水泥和核电工程用水泥的一项关键的技术指标。全球范围内测定水泥水化热的方法有溶解法、直接法/半绝热法、等温传导量热法三种。本文总结了中、美、欧相关方法标准,对其测试原理、仪器设备、试验过程等方面进行了比对,并对其在领域的应用做了简单的概括。     

Measurement of the gradient of viscosity with composition of mixtures of non-ideal gases

A perturbation viscometer is a differential capillary viscometer that measures the logarithmic viscosity gradient of the viscosity-composition curve for gas mixtures. Measurements are made at different gas mixture compositions. Integration of the logarithmic viscosity gradients measured over the full composition range gives the mixture viscosity relative to the viscosity of one of the pure components of the gas mixture. This method is attractive because, for measurements of equal precision, integration of the gradients is potentially an order of magnitude more precise than measurement of the viscosities directly. It can also work at high and low temperatures and perhaps high pressures.The perturbation viscometer has been used to make measurements on ideal gas mixtures at ambient and elevated temperatures. The situation is more complicated when the gas mixtures are non-ideal. Extra effects due to density differences, molar volume change on mixing and differential thermal expansion may be measured in addition to the desired viscosity change producing systematic errors in the results. Thus, a more sophisticated apparatus is required. The standard perturbation viscometer has been modified to separate out the extra effects to permit measurement of the true change in viscosity. In addition, the theoretical operation of the modified apparatus has been revised to account for the design changes to permit calculation of the viscosity-composition profiles from the results.The apparatus has been tested using helium-HFC-125 mixtures and two new viscosity-composition profiles are presented for these mixtures at 23 and . Internal consistency tests have been used to confirm that the data produced are of high quality with an estimated uncertainty in the viscosity ratio data at of 0.9% and at of 1.5%.     

Calorimetric and Computational Study of Enthalpy of Formation of Diperoxide of Cyclohexanone

A thermochemical rather simple experimental technique is applied to determine the enthalpy of formation of Diperoxide of ciclohexanone. The study is complemented with suitable theoretical calculations at the semiempirical and ab initio levels. A particular satisfactory agreement between both ways is found for the ab initio calculation at the 6–311G basis This set level. Some possible extensions of the present procedure are pointed out.     

塔设备改造选型的分析

就当前扩产增容中塔设备设计和改造时板式塔和填料塔的选型问题加以分析。在评述目前国内常用的几种塔板和新型填料之后，着重介绍一种新型塔板（导向梯形浮阀塔板）和一种新型填料（波环填料——乾隆帕克）。     

Effect of degree of deacetylation of chitin on the properties of chitin crystallites

In the present article, chitin from crab shell was systematically deacetylated using a NaOH treatment with control of the reaction time. The degree of deacetylation, monitored using solid-state NMR, revealed that the reaction was pseudo-first order. Based on this, swollen and NaOH-saturated particles are proposed as the reaction system. The weight loss of the partially saponified and neutralized samples after HCl hydrolysis increased linearly with the degree of deacetylation. The crystallinity of the samples was found to increase after acid hydrolysis. According to conductimetric titration, the surface charge density of the crystallites, after acid hydrolysis, was found to increase with base treatment time. The effect of surface charge on the formation of a chiral nematic phase, due to the rodlike nature of the crystallites, was explored. These results show that because the contribution of charged particles to the ionic strength was significant the double layer compression was affected, especially since the surface charge density was close to the Manning limit. © 1997 John Wiley & Sons, Inc. J Appl Polym Sci 65:373–380, 1997