基于水热法制备的TiO_2/MoS_2复合光催化剂及其光催化制氢活性

采用水热法制备出了TiO_2/MoS_2复合光催化剂,通过X射线衍射(XRD)、透射电镜(TEM)、紫外可见漫反射光谱(DRS)、X射线光电子能谱分析(XPS)和光致发光光谱(PL)方法对TiO_2/MoS_2进行表征.研究了MoS_2负载量、复合催化剂TiO_2/MoS_2表面担载的贵金属种类(Pt、Pd、Ru)及其担载量、空穴牺牲剂种类对光催化反应制氢活性的影响,并考察了催化剂的稳定性.研究结果表明,硫化钼和二氧化钛复合能显著提高光催化产氢性能,硫化钼的最佳负载量为5 wt%,比产氢速率为776.99μmol·h~(-1)·g~(-1),其产氢活性是纯TiO_2的4.92倍,商业P25的3.67倍;复合催化剂TiO_2/5 wt%MoS_2表面担载的贵金属种类及其质量分数对产氢性能有一定的影响,其中0.5 wt%的Pd对产氢性能的影响最大,能明显提高复合催化剂的产氢性能,比产氢速率可提高至2599μmol·h~(-1)·g~(-1);该催化剂可利用不同有机物作为牺牲剂产氢,如甲醇、乙醇和乳酸,三者产氢量的次序为:甲醇乳酸乙醇;经过5次循环实验,复合催化剂Pd/(TiO_2/MoS_2)仍能保持90%的活性.另外,对复合催化剂光催化产氢机理也进行了分析.     

FR-CNTs-PbO2/SnO2-Sb/Ti电极性能及电催化降解罗丹明B

利用碳纳米管(CNTs)的优异性能和氟树脂(FR)的憎水性能,采用电化学共沉积法制备掺杂型FR-CNTs-PbO2/SnO2-Sb/Ti复合电极.运用扫描电子显微镜(SEM)和X射线衍射(XRD)仪对该电极的形貌和组成进行表征,采用接触角仪和阳极极化曲线对电极的电化学性能进行考察.结果表明,该电极比FR-PbO2/SnO2-Sb/Ti和PbO2/SnO2-Sb/Ti电极具有更强的憎水性能和更高的O2析出电位,这将有利于提高电极的电催化性能和电流利用效率.将FR-CNTs-PbO2/SnO2-Sb/Ti电极应用于罗丹明B(RhB)的降解研究,30 mA.cm-2电流密度下,处理10μmol.L-1RhB 15 min,RhB去除率高达90.21%.相同条件下,FR-PbO2/SnO2-Sb/Ti电极对RhB的去除率仅为69.08%.且FR-CNTs-PbO2/SnO2-Sb/Ti电极的反应速率常数为0.2215 min-1,是FR-PbO2/SnO2-Sb/Ti电极(k=0.1191 min-1)的近2倍.由此可见,较强的憎水性和较高的析氧电位,增强了FR-CNTs-PbO2/SnO2-Sb/Ti电极的电化学性质和电催化效果.     

Ti~(3+)自掺杂TiO_2纳米管/g-C_3N_4复合材料的制备及可见光催化性能

以低温退火制得的TiO_2纳米管和三聚氰胺为原料,经过一步煅烧制备Ti~(3+)自掺杂TiO_2纳米管/g-C_3N_4复合材料.采用热重分析(TGA)、X-射线衍射(XRD)、透射电子显微镜(TEM)、X-射线光电子能谱(XPS)和紫外-可见漫反射光谱(UV-Vis DRS)对Ti~(3+)自掺杂TiO_2纳米管/g-C_3N_4复合材料的热稳定性、组成、结晶性、形貌、化学价态和光学性能等进行了表征.结果表明,将H_2Ti_3O_7预处理后再与三聚氰胺混合热处理,产物是Ti~(3+)自掺杂TiO_2纳米管/g-C_3N_4复合材料,而未经预处理的H_2Ti_3O_7与三聚氰胺混合后热处理得到的是Ti~(3+)自掺杂TiO_2纳米颗粒/g-C_3N_4复合材料.罗丹明B((RhB)水溶液为模拟废水,以300 W氙灯(λ420 nm)为光源,研究了所得产物的可见光催化降解性能.结果表明,与纯的TiO_2和g-C_3N_4相比,Ti~(3+)自掺杂TiO_2纳米管/g-C_3N_4复合材料具有最佳的光催化降解性能,光催化降解80 min时,对RhB的降解率达98.4%.这得益于Ti~(3+)及TiO_(2-x)纳米管与g-C_3N_4构筑的异质结提高了材料对可见光的响应性能,加快了光生电子的传输和分离,降低了电子和空穴的复合几率.     

铂掺杂二氧化钛的制备及光催化乳酸制氢的研究

采用溶胶-凝胶法和甲醛还原法制备了Pt/TiO2光催化剂,并采用XRD对其结构进行了表征.当焙烧温度为500℃时,制备的纳米二氧化钛为纯锐钛矿相;在二氧化钛表面沉积少量的铂对二氧化钛的晶相和粒径几乎没有影响,但可以使二氧化钛光催化的产氢性能提高近10倍.以乳酸为电子供体,对影响其光催化产氢的因素进行了详细地考察.研究结果表明,光催化分解乳酸产氢的最佳条件为焙烧温度500℃、焙烧时间2 h、载铂量0.8%、催化剂用量0.14 g·L-1和pH 1-2.     

电催化氧化阳极制备及其降酚特性

以自制Ti基SnO2/Sb2O3/IrO2镀层形稳电极(Dimensionless Stable Anode)为阳极,采用电催化氧化法处理模拟含酚废水.通过涂层分析和电化学性能测试表征了自制电极特性,考察了电解质类型和浓度、电流密度、苯酚初始浓度及体系初始pH值等因素对苯酚氧化过程的影响,并探讨其降解动力学规律.结果表明,自制电极是以SnO2为基础的纳米级固熔体氧化物电极且具有较好的表面结构,运行稳定性较好.苯酚的降解主要依赖于以NaCl为电解质时产生的氯系活性物质的间接氧化作用.随着电解质浓度及电流密度的增加,苯酚降解速率随之增大;而苯酚的初始浓度越大,降解速率越慢.体系初始pH对过程影响不明显.苯酚的降解过程符合一级反应动力学。     

氧化石墨烯氧化程度对磷酸铋/石墨烯复合气凝胶光催化活性的影响

三维网络结构磷酸铋/石墨烯复合气凝胶(BiPO_4/GA)可用于有机污染物的吸附富集和原位光催化协同净化.本文采用SEM、FTIR、XRD和紫外-可见漫反射光谱(UV-Vis DRS)系统表征了氧化石墨烯(GO)及其氧化程度对BiPO_4/GA复合材料的形貌、结构、光吸收和光催化性能的影响.氧化程度较高的GO呈棕色,易与BiPO_4形成气凝胶,且BiPO_4纳米棒均匀分散在石墨烯层上.而氧化程度较低的GO颜色较深,合成的BiPO_4/GA复合材料难以保持气凝胶形状.高氧化程度BiPO_4/GA复合材料对苯酚和亚甲基蓝(MB)的降解率分别约为低氧化程度BiPO_4/GA的1.88倍和2.34倍.研究结果表明,通过提高复合材料制备原料GO的氧化程度,可以显著提高BiPO_4/GA气凝胶的光催化活性.光催化机理为BiPO_4/GA气凝胶表面吸附富集有机污染物,光生电子从BiPO_4转移到石墨烯层,并通过催化剂上产生的空穴及超氧自由基(·O_2~-)进行有机物的有效氧化降解.     

g-C3N4/RGO的制备、光催化降解性能及其降解机理

尿素固相反应得到石墨相氮化碳(g-C₃N₄),石墨(G)被氧化制得氧化石墨(GO),GO被还原制得石墨烯(RGO),通过3种复合方法分别制得g-C₃N₄/RGO材料.通过对污染物亚甲基蓝、罗丹明B和甲基橙的降解,考察了g-C₃N₄与GO不同复合比9.7:1、9.3:1、9:1、8:1和6.7:1对光催化剂g-C₃N₄/RGO光催化性能的影响.同时考察了复合物对污染物的选择性降解.用X-射线衍射谱(XRD)和傅里叶变换红外光谱(FT-IR)对催化剂的结构性质进行了表征.结果表明,g-C₃N₄与GO混合-水合肼还原-高温固相反应法制备的g-C₃N₄/RGO,时间最短,产量较高,对罗丹明B的降解效果最佳,说明该方法较好.另外,当g-C₃N₄与GO的质量比为9.7:1时,制备的g-C₃N₄/RGO降解效果最佳.还有,该复合材料对亚甲基蓝的降解效果最佳,罗丹明B次之,甲基橙最差.机理研究结果表明超氧自由基在光催化过程中起主导作用,羟基自由基起次要作用.     

氨及其氧化产物对TiO_2/ACF光催化降解甲苯的影响

利用自制的复合材料二氧化钛/活性炭纤维(TiO2/ACF)和自行设计的环境模拟舱,对吸附在TiO2/ACF上的甲苯和氨进行了光催化降解研究。重点考察了氨及其氧化产物对甲苯光催化降解的影响。结果表明,在254 nm紫外灯照射下,氨与甲苯产生竞争光催化降解效应,甲苯光催化降解效率降低;NO2-和NO3-是氨光催化氧化产物,NO2-进一步氧化抑制甲苯降解,而NO3-的存在对甲苯降解没有明显影响;氨及其氧化产物均未导致催化剂失活。     

AgI/TiO2催化剂的焙烧处理及其可见光催化活性

常温下以TIO2为载体,使用沉积-沉淀法合成了具有不同AgI负载量的AgI/TiO2合光催化剂,并研究了焙烧处理对AgI/TiO2在可见光下(λ＞420nm)催化降解甲基橙(MO)的影响.结果表明,焙烧处理有效提高了AgI/TiO2的光催化性能,当焙烧温度高于200℃时,AgI/TiO2的光催化活性接近并达到最大值.当负载的AgI与TiO2的物质的量之比为0.15时,AgI%TiO2光催化降解MO的效率最高.XRD和UV-Vis测试表明焙烧处理提高了光敏组分AgI混晶中的γ相含量,拓宽了AgI/TiO2在可见光区的吸收范围,提高了光催化活性.     

长寿命Ti/TiO_2/SbO_2-SnO_2/SnO_2-Sb-CeO_2制备及电催化废水性能

使用电镀法制备了含SbO2-SnO2中间层的TiO2/SbO2-SnO2/SnO2-Sb-CeO2电极.采用扫描电镜(SEM)、X射线衍射仪(XRD)、电化学工作站等分析仪器研究了中间层对电极表面结构、组分和电化学性能的影响.在大电流密度下测定了电极的强化使用寿命,并以酸性黑10B为模拟污染物研究了电极的电催化性能.研究结果表明,SbO2-SnO2中间层可有效改善电极表面结构,从而影响电极的寿命和催化性能.相比不含中间层的TiO2/SnO2-Sb-CeO2电极,加入SbO2-SnO2中间层后,电极表面的活性层更加致密和平整,寿命增加了10倍,对酸性黑10B的降解速率提高了一倍.     

Photocatalytic degradation of phosphamidon using Ag-doped ZnO nanorods

The photocatalytic degradation of the organo-phosphorous pesticide phosphamidon at low concentration in aqueous solution on Ag-doped ZnO nanorods was investigated. Nanosized Ag-doped ZnO rods were synthesized by using a microwave assisted aqueous method. High molecular weight polyvinyl alcohol was used as a stabilizing agent. Composition and structure were investigated using energy-dispersive X-ray spectroscopy (EDAX) and X-ray diffraction (XRD). The XRD pattern reveals that ZnO nanorods are of hexagonal wurtzite structure. The average crystallite size calculated from Scherrer's relation was found to be 30?nm. The effects of catalyst loading, pH value, and initial concentration of phosphamidon on the photocatalytic degradation efficiency using Ag-doped ZnO nanorods as a photocatalyst have been discussed. The results revealed that Ag-doped ZnO nanorods with a diameter of 30?nm showed highest photocatalytic activity at a surface density of 1?g?dm^?3. The catalyst doped with 0.2?mol% Ag is effective for the degradation of phosphamidon with visible light. This opens a new possibility to decompose pesticides that are present in wastewater.     

Fe-C-H_2O_2协同催化氧化处理印染废水

用Fe-C-H2O2协同催化氧化体系对印染工业废水的降解脱色处理进行了研究。对影响印染废水降解的几种因素如铁屑/碳粒质量比、双氧水的质量分数、废水pH等进行考察。试验结果表明,对于色度为650度和ρ（COD）为468mg·L-1的印染废水,在废水pH=4.8的情况下,当铁屑/碳粒质量比为25∶1、H2O2用量为150mg·L-1、催化反应30min时,印染废水的脱色率达98%以上,CODCr去除率可达78%。与Fe-C微电解法相比,Fe-C-H2O2协同催化氧化方法对印染废水的脱色能力和去除COD,表现出了更好的处理效果。     

Highly effective visible-photocatalytic hydrogen evolution and simultaneous organic pollutant degradation over an urchin-like oxygen-doped MoS2/ZnIn2S4 composite

● An urchin-like OMS/ZIS composite was fabricated by a facile solvothermal method. ● The OMS/ZIS exhibits superior photocatalytic H₂ evolution for organics degradation. ● A probable mechanism of dual-functional photocatalysis was proposed in detail. ● This work provides an inspiration for rational design of dual-functional catalysts. Achieving hydrogen production and simultaneous decomposition of organic pollutants through dual-functional photocatalytic reactions has received increasing attention due to the environmentally friendly and cost-effective characteristics of this approach. In this work, an urchin-like oxygen-doped MoS₂/ZnIn₂S₄ (OMS/ZIS) composite was fabricated for the first time using a simple solvothermal method. The unique microstructure with abundant active sites and fast charge transfer channels further shortened the charge migration distance and compressed carrier recombination. The obtained composite exhibited an efficient H₂ evolution reaction rate of 12.8 mmol/g/h under visible light, which was nearly times higher than pristine ZnIn₂S₄, and the apparent quantum efficiency was 14.9% (420 nm). The results of the simultaneous photocatalytic H₂ evolution and organic pollutant decomposition test were satisfactory, resulting in decomposition efficiencies of resorcinol, tetracycline, and bisphenol A that reached 41.5%, 63.5%, and 53.0% after 4 h, respectively, and the highest H₂ evolution rate was 672.7 μmol/g/h for bisphenol A. Furthermore, natural organic matter (NOM) abundantly found in actual water was adopted as an electron donor for H production under simulated sunlight irradiation, indicating the promising practicability of simultaneous hydrogen evolution and NOM decomposition. Moreover, the mechanisms of the dual-purpose photocatalytic reactions, as well as the synergistic effect between the molecular structures of the organic pollutants and the corresponding adsorption behavior on the photocatalyst surface were illustrated in detail. These obtained results may serve as an inspiration for the rational design of highly efficient, dual-functional photocatalysts in the future.     

再生气氛对CuO/AC脱硫活性的影响

本文考察了不同气氛再生后ＣｕＯ／ＡＣ脱硫剂的二次脱硫活性，并藉借助ＸＲＤ和ＸＰＳ表征技术以及对再生后脱硫剂残硫的分析，探讨了脱硫剂以不同还原剂在不同温度下再生后二次脱硫活性差异的内在原因，结果表明：脱硫剂经Ｈ２再生后二次脱硫活性与初活性相比出现大幅度下降，Ｈ２气氛中添加Ｈ２Ｏ可提高其二次脱硫活性；经ＮＨ３在３００℃再生后二次脱硫活性与初活性相当，两次再生后仍未观察到活性的明显下降，ＮＨ３再生时脱硫     

暹罗鱼腥藻氢代谢的调节

暹罗鱼腥藻（Ａｎａｂａｅｎａｓｉａｍｅｍｓｉｓ）能代谢分子氢，其固氮酶和氢酶的放氢和吸氢均受其生长环境因子的影响。ＣＯ２对暹罗鱼腥藻之固氮酶的放氢和氢酶的放氢及吸氢显示不同程度的促进作用。在含５％ＣＯ２的空气条件下生长，藻细胞的氢酶放氢和吸氢活位分别为空气条件下的２．５倍和１．３倍；固氮酶的放氢活性为９６ｎｍｏｌＨ２ｍｇ－１ｃｈｌ－１ｈ－１，而在空气中生长的细胞则检测不出该活性，培养基中加１０ｍｍｏｌ／ＬＫＮＯ３和／或１０ｍｍｏｌ／ＬＮａＮＯ２，对其氢酶放氢活性影响不大，但其需氧吸氢和固氮酶的放氢均明显受到抑制。ＤＣＭＵ和Ｋ３Ｆｅ（ＣＮ）６等抑制剂对氢酶活性有不同程度的影响，一些金属离子对氢酶放氢有刺激作用，其中尤以Ｎｉ２＋和Ｍｏ２＋明显。     

Solar photocatalytic decomposition of two azo dyes on multi-walled carbon nanotubes (MWCNTs)/TiO<Subscript>2</Subscript> composites

Multi-walled carbon nanotubes (MWCNTs)/TiO₂ composite photocatalysts with high photoactivity were prepared by sol-gel process and further characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), Fourier transform infrared (FT-IR), and UV-vis absorption spectra. Compared to pure TiO₂, the combination of MWCNTs with titania could cause a significant absorption shift toward the visible region. The photocatalytic performances of the MWCNTs/TiO₂ composite catalysts were evaluated for the decomposition of Reactive light yellow K-6G (K-6G) and Mordant black 7 (MB 7) azo dyes solution under solar light irradiation. The results showed that the addition of MWCNTs enhanced the adsorption and photocatalytic activity of TiO₂ for the degradation of azo dyes K-6G and MB 7. The effect of MWCNTs content, catalyst dosage, pH, and initial dye concentration were examined as operational parameters. The kinetics of photocatalytic degradation of two dyes was found to follow a pseudo-first-order rate law. The photocatalyst was used for seven cycles with photocatalytic degradation efficiency still higher than 98%. A plausible mechanism is also proposed and discussed on the basis of experimental results.     

Sorption-enhanced chemical looping oxidative steam reforming of methanol for on-board hydrogen supply

Hydrogen is an indispensable energy carrier for the sustainable development of human society. Nevertheless, its storage, transportation, and in situ generation still face significant challenges. Methanol can be used as an intermediate carrier for hydrogen supplies, providing hydrogen energy through instant methanol conversion. In this study, a sorption-enhanced, chemical-looping, oxidative steam methanol-reforming (SECL-OSRM) process is proposed using CuO–MgO for the on-board hydrogen supply, which could be a promising method for safe and efficient hydrogen production. Aspen Plus software was used for feasibility verification and parameter optimization of the SECL-OSRM process. The effects of CuO/CH3OH, MgO/CH3OH, and H2O/CH3OH mole ratios and of temperature on H2 production rate, H utilization efficiency, CH3OH conversion, CO concentration, and system heat balance are discussed thoroughly. The results indicate that the system can be operated in auto-thermal conditions with high-purity hydrogen (99.50 vol％) and ultra-low-concentration CO (<50 ppm) generation, which confirms the pos-sibility of integrating low-temperature proton-exchange membrane fuel cells (LT-PEFMCs) with the SECL-OSRM process. The simulation results indicate that the CO can be modulated in a lower concentration by reducing the temperature and by improving the H2O/CH3OH and MgO/CH3OH mole ratios.     

TiO2/粉煤灰的制备及光催化性能研究

以钛酸丁酯为原料,以粉煤灰微珠为载体,采用溶胶-凝胶法制备了TiO2/粉煤灰光催化剂.负载于粉煤灰表面的TiO2平均粒径约为7nm,晶型为锐钛矿型,该催化剂在太阳光下降解初始浓度为10mg·l-1的甲基橙,经6h,甲基橙的降解率可达98.9%,将其应用于实际样品的测定,经3h降解率可达96.1%,显示出优越的光催化降解性能.     

Investigation of the effects of humic acid and H 2 O 2 on the photocatalytic degradation of atrazine assisted by microwave

A solution of atrazine in a TiO₂ suspension, an endocrine disruptor in natural water, was tentatively treated by microwave-assisted photocatalytic technique. The effects of mannitol, oxygen, humic acid, and hydrogen dioxide on the photodegradation rate were explored. The results could be deduced as follows: the photocatalytic degradation of atrazine fits the pseudo-first-order kinetic well with k = 0.0328 s⁻¹, and ·OH was identified as the dominant reactant. Photodegradation of atrazine was hindered in the presence of humic acid, and the retardation effect increased as the concentration of humic acid increased. H₂O₂ displayed a significant negative influence on atrazine photocatalysis efficiency. Based on intermediates identified with gas chromatography-mass spectrometry (GC-MS) and Liquid chromatography-mass spectrometry (LC-MS/MS) techniques, the main degradation routes of atrazine are proposed.     

纳米氧化铜(CuO NPs)对紫花苜蓿幼苗根系活性氧(ROS)、抗氧化酶活性和根系活力的影响

根系通常是植物直接受到外界环境物质(如重金属离子和纳米金属氧化物)毒害的主要器官。本研究以紫花苜蓿的幼苗为实验材料,探讨了CuO NPs胁迫对紫花苜蓿幼苗根系的活性氧(ROS)积累、抗氧化酶活性和根系活力的影响。研究结果表明:(1)不同浓度的CuO NPs对紫花苜蓿幼苗根系H_2O_2和O-2·含量具有显著影响。随CuO NPs浓度增大,紫花苜蓿幼苗根系中H_2O_2和O-2·整体上呈现先增大后减少的趋势,除了0.00125 mol·L~(-1)CuO NPs浓度下紫花苜蓿幼苗根系中H_2O_2含量比对照减少外,其他浓度下的H_2O_2和O-2·的含量都比对照有所增加,并且H_2O_2和O-2·的含量都是在0.0125 mol·L~(-1)CuO NPs浓度下达到最大值。(2)不同浓度的CuO NPs对紫花苜蓿幼苗根系抗氧化酶活性具有显著影响。随CuO NPs浓度增大,紫花苜蓿幼苗根系中SOD、POD、APX和CAT酶的活性都呈现先增大后减少的趋势,其中,SOD和POD、APX、CAT酶的活性分别是在0.00625、0.0125、0.0625 mol·L~(-1)CuO NPs处理下达到最大,表明这些抗氧化酶在清除根系中的活性氧方面表现出较强的协同性和补偿性。(3)不同浓度的CuO NPs对紫花苜蓿幼苗根系活力具有显著的影响。随着CuO NPs浓度的增加,紫花苜蓿幼苗根系活力逐步升高,这是一种生物适应性应激响应的体现。