An expeditious aqueous Suzuki-Miyaura method for the substituted aryl heterocyclics

Palladium-catalyzed cross-coupling reactions utilizing aryl halides have become a widely used strategy for the formation of new carbon-carbon bonds and in particular for the synthesis of biaryls. The replacement of expensive, toxic, and flammable organic solvents by water is highly desirable for reducing costs and for developing environmentally benign synthetic reactions that facilitate catalyst recycling. Herein, we report an efficient Suzuki-Miyaura cross-coupling reaction using a variety of heterocyclic halides in neat water. Employing air- and moisture-stable palladium-phosphinous acid catalyst [(t-Bu)₂P(OH)]₂PdCl₂(POPd) allows formation of substituted aryl heterocyclics in moderate to high yields. The organic cosolvents are not required. The feasibility of catalyst recycling has also been demonstrated.     

Palladium-catalyzed cross-coupling reactions of aryl boronic acids with aryl halides in water

An efficient Suzuki cross-coupling reaction using a variety of aryl halides in neat water was developed. The Pd-catalyzed reaction between aryl bromides or chlorides and phenyl bo-ronic acids was compatible with various functional groups and affords biphenyls in good to excellent yields without requirement of organic cosolvents. The air stability and solubility in water of the palladium-phosphinous acid complexes were considered to facilitate operation of the coupling reaction and product isolation. The reaction conditions including Pd catalyst selection, temperature, base and catalyst recoverability were also investigated.     

Toward cleaner production of hydrogen peroxide in China

Industrial production of hydrogen peroxide by anthraquinone (AO) process in China was briefly introduced. The pathways for cleaner production of hydrogen peroxide were discussed in detail from the viewpoint of process development and design, these included the replacement of Raney-Ni catalyst by highly active and highly selective Pd/Al₂O₃ catalyst, the reduction of raw materials, steam and power consumption, the usage of high boiling point, low water-soluble and low toxic solvents, the regeneration of degradations, the proper treatment of waste gas, water and solids. Because of these innovations and improvements, the AO process with Pd/Al₂O₃ catalyst for producing hydrogen peroxide was certified as a cleaner production technology by the Chinese government.     

活性炭负载铁催化过硫酸盐降解酸性大红3R

采用浸渍-高温煅烧法制备负载型的Fe/活性炭催化剂,利用电镜扫描(SEM)、X射线衍射(XRD)对催化剂进行表征.并以酸性大红3R为目标污染物,用此催化剂研究了过硫酸盐在非均相催化体系的氧化性能.考察了Fe负载量、过硫酸钠用量、催化剂用量、初始污染物浓度等因素对酸性大红3R降解的影响,并对催化剂重复使用性能进行测试.结果表明,Fe负载量为6%时,催化降解效果最好;当Na2S2O8浓度为3.0 g·L-1,催化剂用量1.5 g·L-1,降解3 h时,酸性大红3R去除率达80%以上;催化剂可重复使用5次以上.同时还采用紫外可见、气相色谱-质谱分析其降解的历程.     

包气带水气二相流CO2运移规律

利用土柱实验装置模拟CO₂在土壤中的迁移转化规律,重点研究湿润峰处水、气二相间污染物转化实验土柱长1m,过饱和CO2溶液浓度为748mg/L.分析表明水相运移受对流、弥散、反应及水-气质量传输机制控制,气相运移受对流、扩散和水-气质量传输机制控制.对土柱中水气二相动态条件下的取样方法进行了探索,确定了CO₂在渗透湿润峰水-气二相间分配系数为0.00061,表明水相向气相有一定传输,但不显著.可进一步为低中水平放射性废物地质处置安全评价及固体废物填埋处置环境影响评价提供定量科学依据.     

Formic acid as an alternative reducing agent for the catalytic nitrate reduction in aqueous media

Formic acid was used for the nitrate reduction as a reductant in the presence of Pd:Cu/γ-alumina catalysts. The surface characteristics of the bimetallic catalyst synthesized by wet impregnation were investigated by SEM, TEM-EDS. The metals were not distributed homogeneously on the surface of catalyst, although the total contents of both metals in particles agreed well with the theoretical values. Formic acid decomposition on the catalyst surface, its influence on solution pH and nitrate removal efficacy was investigated. The best removal of nitrate (50 ppm) was obtained under the condition of 0.75 g/L catalyst with Pd:Cu ratio (4:1) and two fold excess of formic acid. Formic acid decay patterns resembled those of nitrate removal, showing a linear relationship between kf (formic acid decay) and k (nitrate removal). Negligible amount of ammonia was detected, and no nitrite was detected, possibly due to buffering effect of bicarbonate that is in situ produced by the decomposition of formic acid, and due to the sustained release of H2 gas.     

Photocatalytic activity of TiO2 containing anatase nanoparticles and rutile nanoflower structure consisting of nanorods

A series of TiO2 with different crystal phases and morphologies was synthesized via a facile hydrothermal process using titanium nbutoxide and concentrated hydrochloric acid as raw materials. The photocatalytic activity of the samples was evaluated by degradation of Methyl Orange in aqueous solution under UV-Visible light irradiation. On the basis of detailed analysis of the characterizing results of high-resolution transmission electron microscopy, X-ray powder diffraction measurements, X-ray photoelectron spectroscopy and Brunauer-Emmett-Teller measurement, it was concluded that the photo-activity of the catalyst is related directly to the 3D morphology and the crystal phase composition. An excellent catalyst should have both a futile 3D flower-like structure and anatase granulous particles. The 3D flower-like structure could enhance light harvesting, as well as the transfer of reactant molecules from bulk solution to the reactive sites on TiO2. In addition, the optimum anatase/rutile phase ratio was found to be 80：20, which is beneficial to the effective separation of the photogenerated electron-hole pairs.     

Effects of tungsten oxide on the activity and thermal stability of a sulfate-derived titania supported platinum catalyst for propane oxidation

A Pt/WO₃/TiO₂ catalyst for propane oxidation was prepared by a stepwise wet impregnation method, and was aged at 800℃ for 5 hr. Compared to the sulfate-derived titania supported catalyst, the introduction of tungsten oxide as stable Bronsted acid sites led to the formation of more metallic platinum active sites at the Pt/WO₃ interface. The dissociation of surface intermediates for propane oxidation was promoted on the WO₃-modified catalyst. This, as well as the inhibition effects of tungsten oxide on the sintering of anatase and the phase transformation to rutile, resulting in a high activity and thermal stability for the Pt/WO₃/TiO₂ catalyst.     

活性炭的表面性质对CeOx/AC催化臭氧氧化水中苯甲酸的影响机制

实验对活性炭(activated carbon,AC)进行了氧改性、氮改性、硫改性和氮-硫共改性,考查AC的表面性质对CeO_x/AC催化臭氧氧化苯甲酸性能的影响.结果表明,相比氧改性活性炭ACO、硫改性活性炭ACS和氮改性活性炭ACN,氮-硫共改性活性炭ACNS由于含氮官能团和含硫官能团的引入,提高了对苯甲酸的吸附性能和催化臭氧氧化性能.采用氮-硫共改性活性炭为载体制备的CeO_x/ACNS催化剂表面Ce~(3+)含量最高,因而具有最高的催化活性,反应30 min,苯甲酸的去除率由单独臭氧氧化的22%提高到88%,TOC的去除率单独臭氧氧化的7%提高到55%.CeO_x/ACNS催化剂具有良好的稳定性,循环使用6次,苯甲酸的去除率仅从88%降低到82%,整个过程中活性组分Ce的流失只占负载量的0.32%,是一种很有应用潜力的臭氧氧化催化剂.     

核壳结构KNbO3@Co(OH)2的制备及其活化过一硫酸盐降解帕珠沙星的研究

制备了以KNbO₃为载体材料的Co（OH）₂复合材料并对其进行了详细的表征,分析了材料的组成成分、组成形态进而确定了其为核壳结构形貌的KNbO₃@Co（OH）₂.利用合成的样品作为催化剂活化过一硫酸盐（peroxymonosulfate,PMS）来降解帕珠沙星（pazufloxacin,PZF）,结果表明制备的催化剂对PZF的去除效率显著增加.讨论了不同初始PMS剂量对降解效率的影响,发现随着PMS增加可活化生成更多的硫酸根自由基（sulfate radicals,SO₄^·-）和羟基自由基（hydroxyl radicals,HO^·）来降解PZF,但继续增大PMS用量降解效率未见明显提升.酸性和中性pH值条件下利于反应活化PMS降解PZF,而碱性体系减缓反应,甚至强碱体系更易形成Co（OH）₂沉淀不利于反应体系中活性组分CoOH⁺的形成,大大抑制了催化性能.此外,在体系中加入淬灭剂叔丁醇（tert-Butanol,TBA）或者乙醇（ethanol,ETOH）进行自由基的淬灭实验,结果表明SO₄^·-自由基为体系降解PZF过程中主要贡献的自由基,而HO^·自由基的贡献较少.催化剂具有较好的稳定性5次循环之后仍能在10 min之内完全去除PZF.本研究提出了新的思路为制备其他载体的Co（OH）₂核壳结构提供参考依据,同时将该催化剂结合高级氧化技术应用到水体新兴有机污染物净化领域具有很好的应用前景.     

Adsorption of herbicide triclopyr on homoionic clays

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Mn/TiO2和Mn-Ce/TiO2低温脱硝催化剂的抗硫性研究

在低温选择性催化还原(SCR)反应条件下考察了烟气残余SO2对Mn/TiO2和Mn-Ce/TiO2催化剂选择性催化还原活性的影响,同时对SO2的影响机理进行了探讨.结果发现,Mn/TiO2催化剂在SO2反应气氛中失活很快,硫铵盐的沉积和活性组分的硫酸化是催化剂失活的重要原因;Ce的加入可以有效地抑制催化剂活性组分的硫酸化,同时还能降低硫酸盐在催化剂表面的稳定性,从而可以提高催化剂的抗硫性.     

Photo-catalytic CO2 reduction using sol–gel derived titania-supported zinc-phthalocyanine

Carbon dioxide was photo-catalytically reduced to produce formic acid in an aqueous solution using visible light irradiation. Titania and zinc-phthalocyanine (ZnPc)-loaded titania were synthesized by a sol–gel method and in situ chemical synthesis technique. The photo-catalytic reactions were conducted in a Pyrex reactor with a visible light irradiating. XRD and DRS revealed that ZnPc was on the TiO₂ surface. The optimum technique was in situ chemical synthesis and the optimum amount of ZnPc loading was 1.0 wt.% for the highest dispersion among catalysts. The formic acid yield of 1.0 wt.% in situ ZnPc/TiO₂ was 978.6 μmol/g catalyst following 10 h of visible light illumination and the conversion was 0.37%. The yield was higher than those of sol–gel TiO₂ and ZnPc/BH-1, whose yields were 321.0 and 756.2 μmol/g catalyst, respectively. Experimental results indicated that the formic acid yield was significantly increased by loading ZnPc. ZnPc has a higher selectivity than metal catalysts for the reduction of CO₂. The photo-catalytic efficiency of ZnPc/TiO₂ was markedly increased because of the lowering re-combination probability for hole–electron pairs.     

等离子体催化降解甲苯途径的原位红外研究

考察了在常温常压条件下,等离子体分别协同SiO₂、Al₂O₃、NiO/Al₂O₃降解甲苯的性能,并从材料的介电常数、对甲苯的吸附性及臭氧分解能力等角度分析了不同活性表现的原因,同时,采用原位红外技术研究了甲苯降解过程中催化剂表面吸附物种的变化.结果表明,当甲苯浓度为100 ppm,气体流量为100 mL·min^-1时,一定范围内,甲苯降解率随着能量密度、介电常数、吸附性及臭氧分解能力的提高而提高.甲苯在催化剂表面的吸附对其降解途径有十分重要的影响:在放电区域中加入SiO₂,甲苯仍然在气相中完成降解;而存在Al₂O₃ 及NiO/Al₂O₃时,甲苯氧化成苯甲酸的过程主要发生在催化剂表面,是甲苯催化降解的关键步骤,苯甲酸在活性位点的积累将降低催化剂的反应活性.     

零价铁-过硫酸盐体系同时去除水中酸性橙7和磷

采用零价铁(ZVI)活化过硫酸盐(PS)同时去除水中酸性橙7(AO7)和磷.ZVI-PS体系可以产生强氧化性的SO·-4和HO·,从而去除水中AO7.同时,ZVI最终转化为Fe3+,因此可以用来去除水中磷.结果表明,ZVI-PS体系在酸性条件下可以有效的同时去除水中AO7和磷.淬灭实验结果表明,硫酸根自由基(SO·-4)对AO7的降解起主要作用.水中共存的阴离子和腐植酸(HA)对AO7和磷的去除均有抑制作用,其对AO7和磷去除的抑制能力排序均为:HCO-3 NO-2 HA NO-3 Cl-.AO7和磷在超纯水中的去除率高于其他实际水体,但反应60 min后,实际水体中AO7和磷的去除率也分别高达80.31%～92.69%和87.54%～100%,因此,该体系对实际水体中AO7和磷的处理有潜在的应用价值.通过紫外-可见分光光谱和GC-MS分析说明,AO7经过偶氮键断键后的中间产物进一步氧化形成含苯环类物质.同时,TOC有所降低,说明部分AO7被矿化为CO2和H2O.     

6-2氟调醇在活性污泥中的降解

为了解6-2氟调醇(6-2 FTOH)在城市污水处理厂活性污泥中的好氧降解规律,利用室内模拟实验装置,研究了6-2FTOH在未经稀释驯化的活性污泥中的降解动力学及降解产物分布.结果表明,6-2 FTOH能被活性污泥快速吸附并发生降解,降解反应符合一级动力学,半衰期为0.9d.降解产物包括6-2氟调酸(6-2 FTCA)、6-2不饱和氟调酸(6-2 FTUCA)、5-3氟调酸(5-3 FTCA)、5-2s氟调醇(5-2s FTOH)和全氟己酸(PFHxA).第28 d实验结束时,6-2 FTOH残留率为5.5％,6-2 FTCA和6-2 FTUCA的最终产率分别为0和1.2％.5-3FTCA、5-2s FTOH、PFHxA最终产率分别为23.4％、17.6％和1.3％.     

Preparation of MnO2 decorated Co3Fe1Ox powder/monolithic catalyst with improved catalytic activity for toluene oxidation

In this paper, KMnO₄ was used to pre-treat Co₃Fe-layered double hydroxides (LDH) precursor to prepare MnO₂ decorated Co₃Fe₁O_x catalyst. The toluene oxidation performance of the catalyst was investigated systematically. The optimized 0.1MnCF-LDO catalyst exhibited the best catalytic performance, and the temperatures of 50% and 90% toluene conversion (T₅₀ and T₉₀) were 218 and 243°C, respectively. The apparent activation energy (E_a) was 31.6 kJ/mol. The characterization results showed that the pre-redox reaction by KMnO₄ could increase the specific surface area, Co³⁺ species amount and oxygen defect concentration of the catalyst, which are the main reason of the improved toluene catalytic activity. Besides, this method was also applied to enhance toluene oxidation of iron mesh based monolithic catalyst. The 0.1MnCF-LDO/Iron mesh (IM) catalyst showed a 90% toluene conversion at around 316°C which was much lower than that of without MnO₂ addition (359°C). In addition, the water resistant of all the catalysts was studied as well, all the samples showed relatively good water resistance. The toluene conversion still remained to be over >80% even in the presence of 10 vol.% water vapor.     

2,4,4'-三溴联苯醚的光降解研究

以固相微萃取(SPME)结合气相色谱(GC)、气相色谱-质谱联用(GC/MS)技术作为分析检测手段,研究光源、有机溶剂、无机盐与腐殖酸对BDE-28光降解的影响,实验结果表明,光源是影响其降解的主要因素,其次,丙酮、铜离子和腐殖酸对其降解的影响较显著.光源对BDE-28光降解速率的影响为300 W汞灯500 W金卤灯100 W汞灯500 W氙灯;有机溶剂对BDE-28降解速率的影响为甲醇/水(1∶1)甲醇己烷甲苯乙腈丙酮;无机离子的影响各有差别:K+、Na+、SO2-4、NO-3、Cl-对BDE-28降解影响不明显,而Fe3+、NH+4促进BDE-28的降解,Fe2+、Cu2+、Br-抑制BDE-28的降解;腐殖酸抑制BDE-28的降解.     

Study on polyepoxysuccinic acid reverse osmosis scale inhibitor

The effectiveness and applicability of polyepoxysuccinic acid (PESA) as a reverse osmosis (RO) scale inhibitor were studied using static and dynamic methods. In the static study, PESA performed very well in the treatment of water samples with various types of scale that commonly exist in RO water (i.e., CaCO₃, CaSO₄, BaSO₄, SrSO₄), showing an average scale inhibition ratio of above 90% at a dosage of 10 mg/L. SEM analysis showed a disordered CaCO₃ crystal in the presence of PESA, suggesting the scale-inhibiting mechanism. In the dynamic experiment, PESA also showed great performance in the treatment of 10 samples of synthetic tap water or sea water with different ion composition (i.e., Ca²⁺, HCO₃^?, Fe³⁺, Al³⁺). After one cycle (7 d) of RO treatment of each sample at full recycle operation mode under a constant pressure of 1×10⁶ Pa, the differences in water permeability and desalination ratio among samples are within 5%, suggesting that PESA is capable of treating waters of different quality, and has a strong resistance to ions that are harmful to scale inhibiting (i.e., Fe³⁺ and Al³⁺). All these results suggest that PESA should be an effective scale inhibitor that is applicable to RO treatment of waters with a wide range of ion compositions.     

不同植被下森林地表系统水相硫的分布与迁移

为了阐明酸雨对森林生态系统水相硫动态分布的影响,在1997~1999年以庐山植物园的针叶林和阔叶林为研究对象,对降雨、透冠水、干流水、渗漏水、径流水及硫通量进行了监测分析。结果表明,降水中SO2-4含量最高值出现在冬季,最低值在夏季;针叶林和阔叶林的透冠水、干流水和渗漏水中的SO2-4含量均高于降水,且透冠水和干流水均表现为春夏季较低、秋冬季较高,径流水变化与之相反;渗漏水针叶林冬季最高,阔叶林春季最高,其他三个季节差异不大;森林生态系统水相硫年际变化呈递增趋势,即1997年1998年1999年,1999年SO2-4浓度与1998和1997年之间差异达显著或极显著水平,而1997年和1998年差异不显著;针叶林的透冠水、干流水、渗漏水中的SO2-4含量均比阔叶林高,而径流水则比阔叶林低,其pH值变化与之相反。针叶林和阔叶林都能够较好的吸收大气沉降中的S,其固定量均高于降水中S的通量,故庐山森林生态系统目前仍是大气S沉降的汇,对酸沉降仍有缓冲作用,但针叶林由于高输入低输出,因此对S的固定能力更强。