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1.
阮曼  赵艳霞  何圣贵 《化学学报》2021,79(4):490-499
在单一原子量分辨水平上研究纳米尺寸过渡金属氧化物团簇(MxOyq)与小分子的反应不仅能够获得氧化物纳米颗粒的反应性随原子组成和尺寸连续变化的演变规律, 而且对认识其结构特征以及表面活性氧物种(如O-•自由基)的产生机制等具有重要意义. 本工作分别采用耦合快速流动反应管和耦合四极质量过滤器-线形离子阱的两套反射式飞行时间质谱研究了不同“氧缺陷指数”(Δ)的氧化钇团簇YxOy- (x≤50,y≤76; Δ≡2y–1–3x, Δ=0~5)和掺杂氟(F)原子团簇Y xOyF- [x≤49,y≤74; Δ≡(2y+1)–1–3x, Δ=1]与 n-C4H10分子的反应. 实验观测到Δ=1系列团簇(Y2O3)NO- (N=1~25)、(Y2O3)NYO2F- (N=1~24)及Δ=4系列团簇(Y2O3)NYO4- (N=1, 3~24)具有氢抽取反应活性, N≥2时其它Δ系列团簇(Δ=0, 2, 3, 5)在相同实验条件下没有表现出明显的反应性. 密度泛函理论研究Δ=1或4系列小尺寸团簇(Y2O3)NYxOyF0,1- (N≤4;x=0, 1)的结构揭示O-•自由基是氢抽取反应的活性位点, 结合实验可推测Δ=1或4系列纳米尺寸团簇(Y2O3)NYxOyF0,1- (x=0, 1)结构中也含有O-•自由基. 这些结果表明Δ=0系列惰性纳米尺寸团簇(Y2O3)NYO2-可以通过吸附一个O2分子发生电子转移生成O-•自由基(O2-+O2→O-•+O2-•), 也可以通过掺入F原子的方式生成O-•自由基(O2-+F→O-•+F-).  相似文献   

2.
采用循环伏安法分析钠盐溶液中U(Ⅵ)的电化学行为, 恒电位电化学还原处理U(Ⅵ), 利用交流阻抗谱分析电化学还原反应中的过程动力学特性, 利用X射线衍射、 扫描电子显微镜和电子能谱等方法分析了U(Ⅵ)的电化学晶化. 结果表明, 在钠盐溶液中, U(Ⅵ)可通过电化学反应先还原成低价的U(V)并进一步还原为U(Ⅳ), U(Ⅳ)一步氧化为U(Ⅵ), U(Ⅳ)/U(Ⅵ)之间的电化学转化过程受扩散控制, 且U(Ⅵ)的电化学电子转移易受环境pH值的影响; 恒电位还原4 h时, 溶液中U(Ⅵ)的去除率可达90%, U(Ⅵ)的结晶固化产物主要以固态的(UO2)6O2(OH)8·6H2O(水铀矿) 和UO2的形式附着在工作电极上.  相似文献   

3.
采用浸渍法制备了不同B2O3负载量(e.g. 5%~20% (w))的Ag/TiO2-B2O3-Al2O3吸附剂。以含硫量为245.36mg(S)/L 的商业柴油作为考察对象,常温常压下采用静态评价进行吸附脱硫性能研究。结果表明,B2O3改性后的Ag/TiO2-Al2O3吸附剂的柴油吸附脱硫活性有了较大提高,当B2O3的负载量为15%时,吸附剂的吸附脱硫活性最高,2%Ag/4%TiO2-15%B2O3-Al2O3 (w)的饱和吸附硫容达到2.36mg(S)/g 吸附剂。这对于未经预处理的商业柴油而言,吸附脱硫活性已经达到较高水平。采用N2物理吸附、O2化学吸附、X射线衍射(XRD)、NH3程序升温脱附(NH3-TPD)、傅里叶红外光谱(FT-IR spectra)、11B核磁共振(11B-NMR)等表征手段对不同负载量B2O3改性Ag/TiO2-Al2O3吸附剂的织构性质、晶相结构和表面酸性的影响进行研究。关联活性测试和表征结果发现,吸附剂的吸附脱硫活性主要与吸附剂的表面弱酸性有关,而B2O3改性在吸附剂表面引入了较多的四配位的BO4物种,能显著增加吸附剂表面弱酸性位点数量,提高吸附剂的吸附脱硫活性。  相似文献   

4.
采用水热法合成了硅酸镁锂(Laponite), 然后利用十六烷基三甲基溴化铵(CTMAB)对其进行有机改性, 研究了改性后的有机硅酸镁锂(CTMABL)对Cr(Ⅵ)的吸附特性. 结果表明, 改性后样品的比表面积和孔容积变小而平均孔径增大. CTMABL样品的d(001)值从改性前的1.23 nm增加到1.79 nm, 表明CTMAB进入Laponite层间. 随着溶液pH值的提高, CTMABL对Cr(Ⅵ)的吸附效率明显下降; pH<8.5时, CTMABL颗粒表面电势为正, 能够与Cr(Ⅵ)阴离子发生静电吸引从而提高吸附效率. 随着固液比增加, 对Cr(Ⅵ)的去除效率迅速上升, 当固液比达到4 g/L后去除效率趋于稳定. 离子强度对Cr(Ⅵ)吸附过程的影响不明显. CTMABL对Cr(Ⅵ)的吸附符合准二级动力学模型, 吸附传质速率受膜扩散和颗粒内扩散过程共同影响. 等温吸附过程符合Langmuir模型, 热力学分析结果表明吸附过程是一个自发的吸热反应. 综合分析认为表面配合作用是主要的吸附机制, 同时静电引力在吸附过程中起到了促进作用.  相似文献   

5.
采用混合酸酐法合成了两种双二苷酰胺(bisdiglycolamide, BisDGA)萃取剂: N,N,N'',N''-四正辛基-N',N″-乙二基-双二苷酰胺(TOE-BisDGA)和N,N,N'',N''-四正辛基-N',N″-间苯二甲基-双二苷酰胺(TOX-BisDGA). 以磺化煤油和正辛醇混合溶液(体积比 90∶10)作稀释剂, 研究了它们在硝酸溶液中对Eu(Ⅲ)和Am(Ⅲ), 以及自身对HNO3的萃取行为. 结果表明, 2种BisDGAs对HNO3均有一定萃取, 当酸度不超过1.0 mol/L时, 二者形成1∶1型的萃合物. 随HNO3浓度增加, Eu(Ⅲ)和Am(Ⅲ)的萃取分配比增加. 相同条件下, TOE-BisDGA对Eu(Ⅲ)和Am(Ⅲ)的萃取能力强于TOX-BisDGA. 斜率分析表明TOE-BisDGA和TOX-BisDGA与Eu(Ⅲ)和Am(Ⅲ)均形成2∶1型的萃合物. 温度升高, 萃取分配比下降, 萃取反应是放热反应. 2种BisDGAs对Eu(Ⅲ)的亲和力强于对Am(Ⅲ)的亲合力, 表明BisDGAs对Eu(Ⅲ)有一定的选择性. 同时, 研究了BisDGAs萃取Eu(Ⅲ)和Am(Ⅲ)的机理, 给出了表观萃取平衡常数和萃取反应热力学函数ΔH, ΔS和ΔG的值. 此外, 还对TOE-BisDGA和TOX-BisDGA与Eu(Ⅲ)形成的配合物进行了红外和紫外光谱分析.  相似文献   

6.
开发高效、稳定的复合光催化材料是当前环境领域的迫切需求。 本文采用溶剂热协同紫外光还原法成功制备了复合光催化材料Ag/NH2-MIL-125(Ti),并通过X射线衍射(XRD)、扫描电子显微镜(SEM)、能谱(EDS)、紫外-可见漫反射光谱(UV-Vis DRS)及X射线光电子能谱(XPS)等技术手段对其形貌、结构及光学性质进行分析,考察了Ag/NH2-MIL-125(Ti)可见光(λ≥420 nm)催化还原Cr(Ⅵ)的性能,并优化了催化剂用量、Cr(Ⅵ)浓度、空穴捕捉剂种类及用量等条件。 结果表明,在最佳条件下,Ag/NH2-MIL-125(Ti)具有良好的吸附及光催化还原Cr(Ⅵ)性能,其吸附及光催化还原率是NH2-MIL-125(Ti)的3.11倍,Ag/NH2-MIL-125(Ti)特殊的“芝麻饼”形貌以及Ag0与NH2-MIL-125(Ti)之间形成的异质结有助于增强复合材料的光催化还原Cr(Ⅵ)的性能。 同时,通过条件实验,提出了光催化还原过程中主要的活性物种以及Cr(Ⅵ) 的还原机理。 本研究将为金属有机骨架(MOFs)复合材料在可见光催化环境修复领域的应用提供理论依据和实验参考。  相似文献   

7.
研究了结冰过程对溶解性有机质(DOM)的4种典型组分草酸、 酒石酸、 苹果酸和柠檬酸还原Cr(Ⅵ)的影响. 结果表明, 在低浓度下Cr(Ⅵ)在水溶液中不能被4种有机酸所还原; 而在冰中, 不同的有机酸对Cr(Ⅵ)的去除均有促进作用, 且去除效果随着有机酸浓度的增大逐渐增强. 4种有机酸的作用效果强弱顺序为草酸>酒石酸>苹果酸>柠檬酸. 通过使用不同浓度的无机盐和无机酸可以改变冰表面上类似液体层的厚度来抑制Cr(Ⅵ)的还原, 作用效果与无机盐种类无关. 溶液的初始pH值和有机酸结构是影响Cr(Ⅵ)还原的重要因素. 实验条件下冷冻浓缩效应的富集倍数至少可达103, 对冰中草酸去除Cr(Ⅵ)有明显的促进作用.  相似文献   

8.
采用浸渍法制备了一系列不同Cr负载量的CrOx-V2O5-WO3/TiO2催化剂, 研究了Cr改性对该催化剂脱硝活性及抗硫性能的影响. 结果表明, Cr的引入使V2O5-WO3/TiO2催化剂的低温NOx去除效果和抗硫性能显著提升. Cr的负载量为3%(以Cr2O3计算质量分数)时, 催化剂具有最佳的低温脱硝活性和N2选择性. 结构表征结果表明, 改性催化剂中Cr元素主要以Cr3+形式存在, Cr的引入使催化剂的氧化性能明显提升, 并使表面弱酸位点、 强酸位点和催化剂表面吸附氧数量增多. XPS分析结果表明, Cr能使催化剂中V5+/V4+比例降低, 促进催化剂中自由电子的迁移. In situ DRIFTs表征结果显示, Cr的引入能促进NO与吸附在Brönsted酸位点上的NH3在低温条件下反应, 从而使催化剂具有更好的低温脱硝活性. UV-Vis光谱分析结果表明, CrOx负载量提高会显著增加高价态Cr的烧结聚集. 同时, 提出了一种选择性催化还原(SCR)反应中Cr-V协同催化的机理.  相似文献   

9.
采用碱溶酸析法提取腐植酸(HA),通过CaCl2对其改性后与Fe3O4进行复合,制备出不同配比的Fe3O4/HA复合吸附剂。利用SEM、BET、FT-IR、XRD分析方法对HA、钙改性HA、Fe3O4/HA复合吸附剂进行了表征,考察了物料配比及吸附时间、pH值、温度、投加量和初始浓度对Ni(Ⅱ)吸附率的影响。结果表明:质量复合比mHA:mFe3O4:mCaCl2为3∶2∶2的Fe3O4/HA复合吸附剂(HA2)对Ni(Ⅱ)吸附效果最佳。当加入0.8 g吸附剂,Ni(Ⅱ)初始浓度为0.1 g·L-1,吸附5 h,pH=5,温度40℃,吸附剂对Ni(Ⅱ)的吸附率为92.57%。复合吸附剂在4次吸附脱附后,对Ni(Ⅱ)的吸附率仍达到52%。吸附过程符合准二级动力学方程和Freundlich吸附等温式。在20℃~40℃条件下,热力学参数ΔG<0、ΔS=37.57 J/(mol·K)、ΔH=11.07 kJ·mol-1,表明该吸附是自发、熵增、吸热的过程。  相似文献   

10.
铁铈氧化物SCR脱硝催化剂的制备及性能   总被引:1,自引:0,他引:1  
采用浸渍法制备了CeO2-Fe2O3/TiO2催化剂,研究了CeO2负载量对其选择催化还原NO性能的影响,并将其中效果最好的催化剂按照同样组分配比采用溶胶凝胶法制备进行比较。采用BET、XRD、SEM和XPS等手段对催化剂进行表征。实验结果表明,采用浸渍法制备的负载10%CeO2、3%Fe2O3的催化剂脱硝效率最优,最高可达96.65%。采用溶胶凝胶法制备催化剂效率更优,最高为99.36%。结果表明,浸渍法和溶胶凝胶法制备的10%-3%CeO2-Fe2O3/TiO2催化剂均具有较大的比表面积、活性成分分散度好、储氧能力强等优点。  相似文献   

11.
The kinetic parameters including the activation energy for crystallization (E), the Avrami parameter (n) and frequency factor (υ) of a glass in the MgO–CaO–SiO2–P2O5–F system were studied using non-isothermal differential thermal analysis (DTA) with regard to small amount of TiO2 additions. It has been shown that the role of TiO2 changes from a glass network former to a glass network modifier with increasing TiO2 content in this system. The kinetic parameters of the crystallizing phases, apatite and wollastonite, indicated changes accompanied with TiO2 additions, implying that the TiO2 is an effective nucleating agent for promoting the crystallization of apatite and wollastonite. The most effective addition is of about 4 wt% TiO2 in this system. The wear rate and friction coefficient decreased from 1.8 ± 0.1 to 0.9 ± 0.2 and 0.87 to 0.77, respectively, when 4 wt% TiO2 was incorporated to the base glass.  相似文献   

12.
Thermal decomposition of mixed ligand thymine (2,4-dihydroxy-5-methylpyrimidine) complexes of divalent Ni(II) with aspartate, glutamate and ADA (N-2-acetamido)iminodiacetate dianions was monitored by TG, DTG and DTA analysis in static atmosphere of air. The decomposition course and steps of complexes [Ni(C5H6N2O2)(C4H5NO4)2−(H2O)2]·H2O, [Ni(C5H6N2O2)(C5H7NO4)2−(H2O)2]·H2O and [Ni(C5H6N2O2)(C6H8N2O5)2−(H2O)2]·1.5H2O were analyzed. The final decomposition products are found to be the corresponding metal oxides. The kinetic parameters namely, activation energy (E*), enthalpy (ΔH*), entropy (ΔS*) and free energy change of decomposition (ΔG*) are calculated from the TG curves using Coats–Redfern and Horowitz–Metzger equations. The stability order found for these complexes follows the trend aspartate > ADA > glutamate.  相似文献   

13.
The heat capacities of NaNO3 and KNO3 were determined from 350 to 800 K by differential scanning calorimetry. Solid-solid transitions and melting were observed at 550 and 583 K for NaNO3 and 406 and 612 K for KNO3, respectively. The entropies associated with the solid-solid transitions were measured to be (8.43± 0.25) J K−1 mole−1 for NaNO3 and (13.8±0.4) J K−1 mole−1 for KNO3. At 298.15 K the values of C0P S0P, {H0(T)-H0(0)}/T and -{G0(T)-H0(0)}/T, respectively, are 91.94, 116.3, 57.73, and 58.55 J K−1 mole−1 for NaNO3 and 95.39, 133.0, 62.93, and 70.02 J K−1 mole−1 for KNO3. Values for S0T, {H0(T)-H0(0)}/T, and -{G0(T)-H0(0)}/T were calculated and tabulated from 15 to 800 K for NaNO3 and KNO3.  相似文献   

14.
In this work, Bi_2Ti_2O_7/TiO_2 composites were synthesized and studied as potential visible-light-activated photocatalysts in the reduction of aqueous Cr(VI). Bi_2Ti_2O_7/TiO_2 composites with tunable compositions were synthesized via a solvothermal-calcination two-step method, simply by changing the molar ratios of Bi(NO_3)_3·5H_2O to tetrabutyl titanate in the reactants. The compositions, structures and optical properties of the as-synthesized Bi_2Ti_2O_7/TiO_2 composites were characterized by X-ray diffraction, field emission scanning electron microscopy and UV–vis diffuse reflectance spectra. The photocatalytic activity of the as-synthesized Bi_2Ti_2O_7/TiO_2 composites was tested in the reduction of aqueous Cr(VI)under visible-light(λ420 nm) irradiation, and compared with that of TiO_2 nanoparticles. It was observed that the as-synthesized Bi_2Ti_2O_7/TiO_2 composites exhibited much higher photocatalytic activity than TiO_2 nanoparticles, and the most efficient composite(300 mg) can achieve the complete reduction of Cr(VI) in 300 mL of 50 mg/L K_2Cr_2O_7 aqueous solution under visible-light(λ420 nm)irradiation in 90 min.  相似文献   

15.
Electrochemical measurements were performed to investigate the effectiveness of cationic surfactants of the N-alkyl quaternary ammonium salt type, i.e. myristyltrimethylammonium chloride (MTACl), cetyldimethylbenzylammonium chloride (CDBACl), and trioctylmethylammonium chloride (TOMACl), as corrosion inhibitors for type X4Cr13 ferritic stainless steel in 2 M H2SO4 solution. Potentiodynamic polarization measurements showed that these surfactants hinder both anodic and cathodic processes, i.e. act as mixed-type inhibitors. It was found that the adsorption of the N-alkyl ammonium ion in 2 M H2SO4 solution follows the Langmuir adsorption isotherm. Plots of log [θ/(1 − θ)] versus log cinh yielded straight lines with a slope, which changed drastically at the critical micelle concentration (CMC) of the surfactants studied. Accordingly, the CMC could be accurately determined from these measurements. The calculated values of the free energy of adsorption ΔGads are, in cases when the charge on the metal surface is negative with respect to the PZC, relatively high what is characteristically for the chemisorption. On the other hand, for positive metal surfaces it is assumed that SO42− anions are adsorbed first, so the cationic species would be limited by the surface concentration of anions. Accordingly ΔGads values were lower in this case and the adsorption is due to merely electrostatic attraction, which is characteristically of physisorption.  相似文献   

16.
The complexes, M[M(C2O4)3xH2 O, where x=4 for M=Cr(III), x=2 for M=Sb(III) and x=9 for M=La(III) have been synthesized and their thermal stability was investigated. The complexes were characterized by elemental analysis, IR and electronic spectral data, conductivity measurement and powder X-ray diffraction (XRD) studies. The chromium(III)tris(oxalato)chromate(III)tetrahydrate (COT), Cr[Cr(C2 O4)3]·4H2O, released water in a stepwise fashion. Removal of the last trace of water was accompanied by a partial decomposition of the oxalate group. Thermal investigation using TG, DTG and DTA techniques in air produced Cr2O3 at 858°C through the intermediate formation of Cr2O3 and CrC2O4 at around 460°C. While DSC study in nitrogen up to 670°C produced a mixture of Cr2O3 and CrC2O4. In antimony(III)tris(oxalato)antimonate(III)dihydrate (AOD), Sb[Sb(C2O4)3]·3H2O the dehydration took place during the decomposition of precursor at 170–290°C and finally at ca. 610°C Sb2 O5 along with trace amounts of Sb2O4 were produced. Trace amount of Sb2O3 and Sb along with Sb2O is proposed as the end product at 670°C of AOD in nitrogen. The oxide La2O3 is formed at 838°C from the study with TG, DTG and DTA in air of lanthanum(III)tris(oxalato)lanthanum(III)nonahydrate (LON), La[La(C2O4)3]·9H2O. Intermediate dioxycarbonate, La2O2CO3 was generated at 526°C prior to its decomposition to lanthanum oxide in air; whereas in N2 the formation of La2(CO3)3 at 651°C was proposed. The thermal parameters have been evaluated for each step of the dehydration and decomposition of COT, AOD and LON using five non-mechanistic equations i.e. Flynn and Wall, Freeman and Carroll, Modified Freeman and Carroll, Coats–Redfern and MacCallum–Tanner equations. Kinetic parameters, such as, E*, ko, ΔH*, ΔS* etc. were also supplemented by DSC studies in nitrogen for all the three complexes. Some of the intermediate species have been identified by analytical and powder XRD studies. Tentative schemes has been proposed for the decomposition of all three compounds in air and nitrogen.  相似文献   

17.
Highly efficient Co3O4/TiO2 monolithic catalysts with enhanced stability were in-situ grown on Ti mesh for CO oxidation,which could completely oxidize CO at 120℃.The comprehensive catalytic performance is competitive to some noble metal catalysts and conventional Co3O4 powder catalysts,which holds great potential toward industrial applications.Meanwhile,the in-situ synthesis strategy of Co3O4/TiO2 monolithic catalysts on flexible mesh substrate in this work can be extended to the development of a variety of oxide-based monolithic catalysts towards diverse catalysis applications.  相似文献   

18.
The hydrothermal reactions of vanadium oxide starting materials with divalent transition metal cations in the presence of nitrogen donor chelating ligands yield the bimetallic cluster complexes with the formulae [{Cd(phen2)2V4O12]·5H2O (1) and [Ni(phen)3]2[V4O12]·17.5H2O (2). Crystal data: C48H52Cd2N8O22V4 (1), triclinic. a=10.3366(10), b=11.320(3), c=13.268(3) Å, =103.888(17)°, β=92.256(15)°, γ=107.444(14)°, Z=1; C72H131N12Ni2O29.5V4 (2), triclinic. a=12.305(3), b=13.172(6), c=15.133(4), =79.05(3)°, β=76.09(2)°, γ=74.66(3)°, Z=1. Data were collected on a Siemens P4 four-circle diffractometer at 293 K in the range 1.59° <θ<26.02° and 2.01°<θ<25.01° using the ω-scan technique, respectively. The structure of 1 consists of a [V4O12]4− cluster covalently attached to two {Cd(phen)2}2+ fragments, in which the [V4O12]4− cluster adopts a chair-like configuration. In the structure of 2, the [V4O12]4− cluster is isolated. And the complex formed a layer structure via hydrogen bonds between the [V4O12]4− unit and crystallization water molecules.  相似文献   

19.
采用溶胶-凝胶法制备了不同Pr掺杂量的Pr6O11-TiO2载体, 并以浸渍法制备了V2O5-MoO3/Pr6O11-TiO2催化剂. 活性评价结果表明, 该催化剂在220~400 ℃范围内具有良好的脱硝效率和N2选择性以及较强的抗SO2和H2O性能. 表征结果表明, 掺杂Pr可以提高V2O5-MoO3/TiO2催化剂的比表面积、 表面化学吸附氧物种浓度、 桥式硝酸盐物种和Brönsted酸位数量, 从而提高了催化剂上NOx的选择性催化还原(NH3-SCR)活性.  相似文献   

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