Activity and hydrothermal stability of CeO2–ZrO2–WO3 for the selective catalytic reduction of NOx with NH3

A series of CeO_2–ZrO_2–WO_3(CZW)catalysts prepared by a hydrothermal synthesis method showed excellent catalytic activity for selective catalytic reduction(SCR)of NO with NH_3 over a wide temperature of 150–550°C.The effect of hydrothermal treatment of CZW catalysts on SCR activity was investigated in the presence of 10% H_2O.The fresh catalyst showed above 90% NO_x conversion at 201–459°C,which is applicable to diesel exhaust NO_x purification(200–440°C).The SCR activity results indicated that hydrothermal aging decreased the SCR activity of CZW at low temperatures(below 300°C),while the activity was notably enhanced at high temperature(above 450°C).The aged CZW catalyst(hydrothermal aging at 700°C for 8 hr)showed almost 80% NO_x conversion at 229–550°C,while the V_2O_5–WO_3/TiO_2 catalyst presented above 80% NO_x conversion at 308–370°C.The effect of structural changes,acidity,and redox properties of CZW on the SCR activity was investigated.The results indicated that the excellent hydrothermal stability of CZW was mainly due to the CeO_2–ZrO_2 solid solution,amorphous WO_3 phase and optimal acidity.In addition,the formation of WO_3 clusters increased in size as the hydrothermal aging temperature increased,resulting in the collapse of structure,which could further affect the acidity and redox properties.     

Layered sphere-shaped TiO2 capped with gold nanoparticles on structural defects and their catalysis of formaldehyde oxidation

We describe here a one-step method for the synthesis of Au/TiO₂ nanosphere materials, which were formed by layered deposition of multiple anatase TiO₂ nanosheets. The Au nanoparticles were stabilized by structural defects in each TiO₂ nanosheet, including crystal steps and edges, thereby fixing the Au–TiO₂ perimeter interface. Reactant transfer occurred along the gaps between these TiO₂ nanosheet layers and in contact with catalytically active sites at the Au–TiO₂ interface. The doped Au induced the formation of oxygen vacancies in the Au–TiO₂ interface. Such vacancies are essential for generating active oxygen species (*O⁻) on the TiO₂ surface and Ti^3 + ions in bulk TiO₂. These ions can then form Ti^3 +–O⁻–Ti^4 + species, which are known to enhance the catalytic activity of formaldehyde (HCHO) oxidation. These studies on structural and oxygen vacancy defects in Au/TiO₂ samples provide a theoretical foundation for the catalytic mechanism of HCHO oxidation on oxide-supported Au materials.     

Effects of WOx modification on the activity, adsorption and redox properties of CeO2 catalyst for NOx reduction with ammonia

A series of WO₃/CeO₂ (WOx/CeO₂) catalysts were synthesized by wet impregnation of ammonium metatungstate on a CeO₂ support. The resulting solid acid catalysts were characterized by X-ray diffraction (XRD), UV-Vis spectroscopy (UV-Vis), Raman spectroscopy (Raman), in-situ Fourier transform infrared spectroscopy (in-situ FT-IR) of ammonia adsorption, NH₃-TPD, H₂ temperature-programmed reduction (H₂-TPR), NH₃/NO oxidation and activity measurements for NOx reduction by NH₃ (NH₃-SCR). The results show that polytungstate (WOx) species are the main species of tungsten oxide on the surface of ceria. The addition of tungsten oxide enhances the Brönsted acidity of ceria catalysts remarkably and decreases the amount of surface oxygen on ceria, with strong interaction between CeO₂ and WOx. As a result, the N₂ selectivity of NH₃ oxidation and NH₃-SCR at high temperatures (> 300℃) is enhanced. Therefore, a wide working temperature window in which NOx conversion exceeds 80% (NOx conversion > 80%) from 200 to 450℃, is achieved over 10 wt.% WOx/CeO₂ catalyst. A tentative model of the NH₃-SCR reaction route on WOx/CeO₂ catalysts is presented.     

Cu-Al2O3中骨架铜类芬顿催化去除水中有机污染物

为解决传统铁基芬顿催化剂在水体通常酸碱(pH6)条件下活性低的问题,采用简单共沉淀法制备了Cu掺杂的Al_2O_3类芬顿催化剂.通过X射线衍射(XRD)、X射线光电子能谱(XPS)和紫外可见(UV-vis)吸收光谱分析表明,Cu-Al_2O_3中铜掺杂的质量分数低于4.77%时,催化剂中铜主要以Cu~(2+)和Cu~+的形式共存于Al_2O_3的骨架结构中,形成Al—O—Cu键;过量的铜掺杂会导致外骨架铜物种如铜氧化物团簇的存在.以难降解有机污染物2-氯苯酚(2-chlorophenol,2-CP)和染料罗丹明B(Rhodamine B,Rh B)为目标污染物,对Cu-Al_2O_3的类芬顿催化性能进行了详细地研究.结果表明,骨架铜物种在中性温和条件下对2-CP和Rh B显示出很高的催化去除效率和稳定性,反应2 h,Cu-Al_2O_3(Cu质量分数4.77%)对2-CP的去除率达到54%,相应的TOC去除率达到49%,而铜离子溶出浓度仅为0.025 5 mg·L-1,而Cu-Al_2O_3(Cu质量分数7.58%)由于外骨架铜的存在导致催化活性增加缓慢和稳定性下降.ESR测试结果表明,·OH和HO_2~-/O_2~-·是反应中主要的活性物种.     

可见光响应手性TiO2复合光催化剂及其降解有机污染物

通过空穴和自由基捕获剂的加入,首先研究了可见光激发下手性TiO₂复合光催化剂降解罗丹明B和四环素的机理. 结果表明,可见光激发TiO₂光催化剂降解罗丹明B和四环素的机理是相同的,其形成的光生空穴是降解有机物的关键影响因素.利用D型手性表面活性剂在低温时可以构建右旋非对称手性堆积结构的D-TiO₂. 这种非对称结构在介孔TiO₂内部引入氧空穴和Ti-N键,使D-TiO₂也具有显著的可见光响应和可见光降解活性. La³⁺ 或者Fe³⁺的掺杂几乎不影响催化剂的形貌及其TiO₂的结晶过程, 但可以在催化剂中形成光生空穴和电子的捕获中心,显著提升可见光激发下TiO₂催化剂中光生空穴和电子的分离率,从而增强催化剂对四环素的光降解活性.     

Choice of precipitant and calcination temperature of precursor for synthesis of NiCo2O4 for control of CO–CH4 emissions from CNG vehicles

Compressed natural gas(CNG)is most appropriate an alternative of conventional fuel for automobiles.However,emissions of carbon-monoxide and methane from such vehicles adversely affect human health and environment.Consequently,to abate emissions from CNG vehicles,development of highly efficient and inexpensive catalysts is necessary.Thus,the present work attempts to scan the effects of precipitants(Na_2CO_3,KOH and urea)for nickel cobaltite(Ni Co_2O_4)catalysts prepared by co-precipitation from nitrate solutions and calcined in a lean CO-air mixture at 400°C.The catalysts were used for oxidation of a mixture of CO and CH_4(1:1).The catalysts were characterized by X-ray diffractometer,Brunauer–Emmett–Teller surface-area,X-ray photoelectron spectroscopy;temperature programmedreductionandScanningelectronmicroscopycoupledwith Energy-Dispersive X-Ray Spectroscopy.The Na_2CO_3was adjudged as the best precipitant for production of catalyst,which completely oxidized CO-CH_4mixture at the lowest temperature(T_(100)=350°C).Whereas,for catalyst prepared using urea,T_(100)=362°C.On the other hand the conversion of CO-CH_4mixture over the catalyst synthesized by KOH limited to 97%even beyond 400°C.Further,the effect of higher calcination temperatures of 500 and600°C was examined for the best catalyst.The total oxidation of the mixture was attained at higher temperatures of 375 and 410°C over catalysts calcined at 500 and 600°C respectively.Thus,the best precipitant established was Na_2CO_3and the optimum calcination temperature of 400°C was found to synthesize the Ni Co_2O_4catalyst for the best performance in CO-CH_4oxidation.     

沙尘天气对兰州市PM10中主要水溶性离子的影响

利用在线监测仪器MARGA在兰州大学盘旋路校区对兰州市大气PM10中水溶性离子进行监测,监测期间(2011-04-01~2011-06-30)有15 d出现沙尘天气.兰州市PM10中主要水溶性离子物种为Ca2+、SO2-4和NO-3.扬沙天气期间NO-3和NH+4的浓度比非沙尘期间低,说明沙尘天气对当地人为源所排放污染物具有清除作用.沙尘天气期间,作为土壤污染源标识物的Mg2+、Na+和Ca2+离子都有明显增加,Na+和Mg2+相关系数为0.520,Na+和Ca2+相关系数为0.659,Mg2+和Ca2+相关系数为0.671,而非沙尘天气期间三者的相关系数并不高,Na+和Mg2+相关系数为0.065,Na+和Ca2+相关系数为0.131,Mg2+和Ca2+相关系数为0.163,说明沙尘天气期间三者之间具有相同的污染源,主要来自于土壤风沙尘,而非沙尘天气期间三者来源不同.Cl-的浓度在扬沙天气明显高于浮尘和非沙尘天气期间,说明外来的土壤风沙尘是Cl-的主要来源.     

N-doped CoAl oxides from hydrotalcites with enhanced oxygen vacancies for excellent low-temperature propane oxidation

A series of nitrogen-doped CoAlO (N-CoAlO) were constructed by a hydrothermal route combined with a controllable NH₃ treatment strategy. The effects of NH₃ treatment on the physico-chemical properties and oxidation activities of N-CoAlO catalysts were investigated. In comparison to CoAlO, a smallest content decrease in surface Co³⁺ (serving as active sites) while a largest increased amount of surface Co²⁺ (contributing to oxygen species) are obtained over N-CoAlO/4h among the N-CoAlO catalysts. Meanwhile, a maximum N doping is found over N-CoAlO/4h. As a result, N-CoAlO/4h (under NH₃ treatment at 400°C for 4 hr) with rich oxygen vacancies shows optimal catalytic activity, with a T₉₀ (the temperature required to reach a 90% conversion of propane) at 266°C. The more oxygen vacancies are caused by the co-operative effects of N doping and suitable reduction of Co³⁺ for N-CoAlO/4h, leading to an enhanced oxygen mobility, which in turn promotes C₃H₈ total oxidation activity dominated by Langmuir-Hinshelwood mechanism. Moreover, in situ diffuse reflectance infrared Fourier transform spectroscopy (DRIFTs) analysis shows that N doping facilities the decomposition of intermediate species (propylene and formate) into CO₂ over the catalyst surface of N-CoAlO/4h more easily. Our reported design in this work will provide a promising way to develop abundant oxygen vacancies of Co-based catalysts derived from hydrotalcites by a simple NH₃ treatment.     

Synergistic effect of N- and F-codoping on the structure and photocatalytic performance of TiO2

Three types of TiO₂ nanostructures were synthesized via a facile hydrolysis method at 195 °C. Effects of the preparation method and doping with N and F on the crystal structure and photocatalytic performance of TiO₂ were investigated. The nanomaterials were characterized by X-ray diffraction, transmission electron microscopy, X-ray photoelectron spectroscopy, Brunauer–Emmett–Teller porosimetry, ultraviolet–visible diffuse reflectance spectroscopy and fluorescent emission spectra. Their photo-catalytic activity was examined by the photodegradation of methylene blue in aqueous solution under both ultra-violet and visible light irradiation. The results show that nitrogen and fluorine co-doped anatase TiO₂ had the characteristics of a smaller crystalline size, broader light absorption spectrum and lower charge recombination than pure TiO₂. Most importantly, more efficient photocatalytic activity under both ultra-violet and visible light was observed. The obtained N–F-TiO₂ nanomaterial shows considerable potential for water treatment under sunlight irradiation.     

钯掺TiO2光催化降解全氟辛酸

全氟辛酸(perfluorooctanoic acid,PFOA)以其分布广泛性、生物蓄积性、生物毒性强而成为全球关注的一种新型持久性有机污染物.采用化学还原法制备钯掺二氧化钛(Pd-Ti O2)催化剂,利用XRD、FESEM、UV-vis DRS对催化剂进行表征,并考察其在365 nm紫外光照射下对PFOA的光催化降解效果.结果表明,化学还原的制备方法使Ti O2粒径减小、比表面积增大且对紫外光的吸收性能增大,但并不引起PFOA光催化效果的改变.而Pd掺杂后大大增强了PFOA的降解效果,反应7 h后溶液中氟离子浓度为6.62 mg·L-1,是Ti O2(P25)的7.3倍.投加俘获剂与通入氮气的实验证明,在PFOA的降解过程中·OH起重要作用,氧气的存在可促进PFOA的降解.采用UPLC-QTOF-MS对产物进行鉴定分析,PFOA的可能降解过程是经h+氧化后发生脱羧基反应,产生的全氟烷烃自由基(·CnF2n+1)被·OH氧化,脱氟生成短链全氟羧酸.Pd能作为电子(e-)捕获剂、加速e-向O2等电子受体的转移,从而缓解e-累积,提高对PFOA的降解效果.     

卫河新乡市区段春季溶解CH4与N2O浓度特征

对卫河新乡市区段春季CH_4与N_2O浓度进行调查分析,初步探讨了城市河流中典型温室气体的溶存量空间变化及其影响因素.结果表明,受到水中污染物质浓度及人类活动影响,春季卫河表层水中CH_4与N_2O浓度处于超饱和状态,饱和度分别为147.59~2 667.85和4.06~188.25.影响市区内N_2O浓度的主要环境因素为NH~+_4-N(P0.01),而新区污水处理厂排水输入显著提高了N_2O的溶存量,说明污染物类型影响温室气体的产生和积累,NH~+_4-N的硝化过程是城市河流N_2O产生的主要来源.逐步回归分析表明CH_4浓度是NH~+_4-N浓度与水温的相关函数,其中CH_4浓度与NH~+_4-N极显著相关(R2=0.70,P0.01),说明春季卫河中NH~+_4-N浓度是影响卫河春季CH_4溶存的关键因素.此外研究结果显示在NO~-_3-N浓度较低并且NH~+_4-N浓度高时水中CH_4与N_2O浓度具有显著正相关关系,表明有效态氮浓度差异影响CH_4与N_2O产生过程的耦合机制.     

Enhanced catalytic complete oxidation of 1,2-dichloroethane over mesoporous transition metal-doped γ-Al2O3

High-surface-area mesoprous powders of γ-Al₂O₃ doped with Cu^2 +, Cr^3 +, and V^3 + ions were prepared via a modified sol–gel method and were investigated as catalysts for the oxidation of chlorinated organic compounds. The composites retained high surface areas and pore volumes comparable with those of undoped γ-Al₂O₃ and the presence of the transition metal ions enhanced their surface acidic properties. The catalytic activity of the prepared catalysts in the oxidation of 1,2-dichloroethane (DCE) was studied in the temperature range of 250–400°C. The catalytic activity and product selectivity were strongly dependent on the presence and the type of dopant ion. While Cu^2 +- and Cr^3 +-containing catalysts showed 100% conversion at 300°C and 350°C, V^3 +-containing catalyst showed considerably lower conversion. Furthermore, while the major products of the reactions over γ-alumina were vinyl chloride (C₂H₃Cl) and hydrogen chloride (HCl) at all temperatures, Cu- and Cr-doped catalysts showed significantly stronger capability for deep oxidation to CO₂.     

g-C3N4在可见光下协同PDS降解磺胺二甲嘧啶的机制研究

以二聚氰胺为前驱体合成光催化剂石墨相碳化氮(g-C_3N_4),通过透射电子显微镜(TEM)、X射线衍射(XRD)和紫外可见漫反射光谱(UV-vis DRS)等技术对g-C_3N_4材料进行形貌结构和光学性能的表征.实验过程中,以g-C_3N_4光催化降解磺胺二甲嘧啶(SMZ)中,加入过硫酸盐(PDS)联合效果的研究结果表明,PDS加快了g-C_3N_4对SMZ的光催化降解;通过荧光测试,表明了PDS使g-C_3N_4的光生空穴(h~+)与光生电子(e-)能够进行有效地分离,从而加强其光催化性能;实验同时研究了PDS/g-C_3N_4体系对磺胺二甲嘧啶(SMZ)光催化降解的影响机制.研究表明,SMZ的光催化降解反应符合准一级动力学规律;pH在酸性环境下有利于SMZ的降解;使用草酸钠作为光生空穴分子捕获剂,检测到h~+存在于PDS/g-C_3N_4光催化体系中,并计算得出h~+的贡献率为65.9%,表明h~+在降解中起到主要作用;TOC的检测表明,加入PDS有助于SMZ的矿化.     

氧掺杂g-C3N4光催化降解Cu-EDTA络合物的反应机理研究

本研究以Cu-EDTA为模拟污染物,探讨了非金属石墨相氮化碳(g-C_3N_4)在光催化降解重金属络合污染物中的应用潜力.首先采用在空气气氛下煅烧的方式对g-C_3N_4进行氧掺杂改性,并通过XRD、TEM和DRS等表征手段对掺杂前后的催化剂结构进行表征.光催化性能评价结果表明,氧掺杂改性更有利于催化剂表面光生空穴的分离,从而呈现出显著提升的破络合能力.通过自由基猝灭实验对g-C_3N_4光降解Cu-EDTA的催化机制进行了研究,结果表明,未掺杂g-C_3N_4通过O_2~(·-)、空穴和·OH的共同作用实现重金属络合物的去除,而氧掺杂样品以具有更强破络合能力的光生空穴为主要活性物种实现Cu-EDTA污染物的降解.     

Optimization of CO2 adsorption capacity and cyclical adsorption/desorption on tetraethylenepentamine-supported surface-modified hydrotalcite

The objective of this research was to investigate CO_2adsorption capacity of tetraethylenepentamine-functionalized basic-modified calcined hydrotalcite(TEPA/b-c HT)sorbents at atmospheric pressure formed under varying TEPA loading levels,temperatures,sorbent weight to total gaseous flow rate(W/F)ratios and CO_2concentrations in the influent gas.The TEPA/b-c HT sorbents were characterized by means of X-ray diffraction(XRD),Fourier transform infrared spectrometry(FT–IR),thermal gravimetric analysis(TGA),Brunauer–Emmet–Teller(BET)analysis of nitrogen(N_2)adsorption/desorption and carbon–hydrogen–nitrogen(CHN)elemental analysis.Moreover,a full 2~4factorial design with three central points at a 95%confidence interval was used to screen important factor(s)on the CO_2adsorption capacity.It revealed that85.0%variation in the capacity came from the influence of four main factors and the15.0%one was from their interactions.A face-centered central composite design response surface method(FCCCD–RSM)was then employed to optimize the condition,the maximal capacity of 5.5–6.1 mmol/g was achieved when operating with a TEPA loading level of 39%–49%(W/W),temperature of 76–90°C,W/F ratio of 1.7–2.60(g·sec)/cm~3and CO_2concentration of 27%–41%(V/V).The model fitted sufficiently the experimental data with an error range of±1.5%.From cyclical adsorption/desorption and selectivity at the optimal condition,the 40%TEPA/b-c HT still expressed its effective performance after eight cycles.     

Cu(II), Fe(III) and Mn(II) combinations as environmental stress factors have distinguishing effects on Enterococcus hirae

Pollution by various heavy metals as environmental stress factors might affect bacteria. It was established that iron (Fe(III)), manganese (Mn(II)) and copper (Cu(II)) ion combinations caused effects on Enterococcus hirae that differed from the sum of the effects when the metals were added separately. It was shown that the Cu^2 +–Fe^3 + combination decreased the growth and ATPase activity of membrane vesicles of wild-type E. hirae ATCC9790 and atpD mutant (with defective F_oF₁-ATPase) MS116. Addition of Mn^2 +–Fe^3 + combinations within the same concentration range had no effects on growth compared to control (without heavy metals). ATPase activity was increased in the presence of Mn^2 +–Fe^3 +, while together with 0.2 mmol/L N,N′-dicyclohexylcarbodiimide (DCCD), ATPase activity was decreased compared to control (when only 0.2 mmol/L DCCD was present). These results indicate that heavy metals ion combinations probably affect the F_OF₁-ATPase, leading to conformational changes. Moreover the action may be direct or be mediated by environment redox potential. The effects observed when Fe^3 + was added separately disappeared in both cases, which might be a result of competing processes between Fe^3 + and other heavy metals. These findings are novel and improve the understanding of heavy metals ions effects on bacteria, and could be applied for regulation of stress response patterns in the environment.     

纳米零价铁改性生物炭对水中氨氮的吸附特性及机制

传统生物炭材料对水中氨氮(NH⁺₄-N)的吸附效果不佳.以生物炭为载体负载纳米零价铁制得生物炭基纳米零价铁复合吸附剂nZVI@BC,通过吸附实验,考察nZVI@BC对NH⁺₄-N的吸附特性,并采用SEM-EDS、 BET、 XRD和FTIR分析nZVI@BC的组成和结构特性,探讨nZVI@BC吸附NH⁺₄-N的主要机制.结果表明,在298K下铁/生物炭质量比为1∶30时制备的复合吸附剂(nZVI@BC1/30)对NH⁺₄-N的吸附性能最佳,比负载前生物炭的吸附量提高了45.96%,饱和吸附量可达16.60 mg·g^-1.伪二级动力学模型和Langmuir模型更符合nZVI@BC1/30对NH⁺₄-N的吸附过程.共存阳离子与NH⁺₄-N之间存在竞争吸附,其对nZVI@BC1/30吸附NH⁺     

超薄g-C3N4在可见光下协同PDS降解双氯芬酸钠的机理研究

运用一步热聚合法成功制备出二维超薄g-C_3N_4(UCN)纳米片,通过透射电子显微镜、比表面测定仪、紫外可见漫反射光谱、荧光光谱对UCN的形貌及光学性能进行表征,并利用g-C_3N_4对水相中的双氯芬酸钠(DCF)进行了光催化降解实验.结果表明,UCN具有二维超薄纳米片结构,且具有较高的比表面积、较强的可见光吸收能力及空穴-电子转移能力.UCN的光催化活性优于块状g-C_3N_4,过硫酸盐(PDS)的加入对双氯芬酸钠的降解有促进作用,UCN/PDS体系中对双氯芬酸钠降解起主导作用的活性物种为O【math203z】,经过150 min的反应,双氯芬酸钠的矿化率达到78%.双氯芬酸钠在UCN/PDS体系下的光催化降解符合一级动力学规律和Langmuir-Hinshelwood模型,DCF的光催化降解在偏酸和偏碱性的情况下具有较快的反应速率.DCF在河水中的反应速率是超纯水中的3.4倍.循环实验表明,UCN具有很好的光催化稳定性.     

浙江宁波天童地区酸性降水化学特征研究

为了解浙江宁波天童地区降水的化学特征、离子来源及酸性降水的成因,于2010年3月—2011年2月在该地区采集了90个降水样品,并运用离子色谱法分析其化学组分.结果显示,天童地区降水的酸化频率和酸化程度非常高,酸雨频率为97%,雨量加权pH平均值为4.37,离子浓度的大小顺序为SO24->NH4+>NO3->Ca2+>Cl->Na+>Mg2+>K+>F-,降水较清洁;降水pH值和各离子含量存在明显的季节变化,总体表现为冬、春季污染程度高于夏、秋季;SO24-/NO3-的浓度比值为1.9,表明该地区酸雨类型为硫酸和硝酸复合型;SO24-、NO3-、NH4+和部分Ca2+主要来自人为污染源,Na+、Cl-和大部分Mg2+主要来自海洋源,K+和大部分Ca2+则主要来自地壳源,海洋对天童地区降水离子组分影响较大,但对降水酸度影响并不显著;NH4+与SO42-(r=0.90)、NO3-(r=0.88)的相关性分别大于Ca2+与SO24-(r=0.67)、NO3-(r=0.73)的相关性,且NH4+/Ca2+的浓度比值为1.47,说明NH4+对降水酸性的中和作用大于Ca2+,与我国其他城市降水相比,天童地区降水中的碱性离子,尤其是Ca2+浓度较低,从而导致降水酸度高于北方地区和西南其他地区.