Improving the activity of Mn/TiO2 catalysts through control of the pH and valence state of Mn during their preparation

In this study, the authors investigated the influence of the valence state of Mn on the efficacy of selective catalytic reduction using a Mn-based catalyst. The nitrogen oxides (NO_x) conversion rate of the catalyst was found to be dependent on the type of TiO₂ support employed and on the temperature, as the catalyst showed an excellent conversion of > 80% at a space velocity of 60,000 hr^?1 when the temperature was above 200 °C. Brunauer-Emmett-Teller, X-ray diffraction, and X-ray photoelectron spectroscopy analyses confirmed that catalyst displaying the highest activity contained the Mn⁴⁺ species and that its valence state was highly dependent on the pH during the catalyst preparation.

Implications Recently, various Mn catalysts have been evaluated as selective catalyst reduction (SCR) catalysts. However, in these previous studies, only the reaction characteristics and catalytic activity on the NH₃ SCR over Mn catalysts were evaluated. There have been no studies on the effect of pH during catalyst preparation. Therefore, in this study, the effect of pH during the catalyst preparation process was examined and a new application of the Mn catalysts was proposed based on the current findings.     

制备工艺对V2O5/TiO2 SCR催化剂脱硝性能的影响

围绕SCR脱硝催化剂制备工艺中活性组分负载顺序和钒助溶剂2个关键因素,分别制备了钒钨体系和钒钼体系催化剂,比较了不同条件下制备的催化剂的脱硝活性,并利用X射线光电子能谱分析（XPS）、程序升温还原（H2-TPR）和程序升温脱附（NH3-TPD）等手段进行表征。结果表明,活性组分与助剂同时负载制备的催化剂,其低价钒和化学吸附氧的比例最高,钒的还原温度最低,酸性位数量最多,表现出最好的脱硝活性;相较于常规助溶剂单乙醇胺,以草酸为助溶剂制备的催化剂,其低价钒和化学吸附氧比例更高,氧化还原性能和表面酸性更强,脱硝活性更好。     

Effect of the Mn oxidation state and lattice oxygen in Mn-based TiO2 catalysts on the low-temperature selective catalytic reduction of NO by NH3

TiO₂-supported manganese oxide catalysts formed using different calcination temperatures were prepared by using the wet-impregnation method and were investigated for their activity in the low-temperature selective catalytic reduction (SCR) of NO by NH₃ with respect to the Mn valence and lattice oxygen behavior. The surface and bulk properties of these catalysts were examined using Brunauer-Emmett-Teller (BET) surface area, X-ray diffraction (XRD), temperature-programmed reduction (TPR), and temperature-programmed desorption (TPD). Catalysts prepared using lower calcination temperatures, which contained Mn⁴⁺, displayed high SCR activity at low temperatures and possessed several acid sites and active oxygen. The TPD analysis determined that the Brönsted and Lewis acid sites in the Mn/TiO₂ catalysts were important for the low-temperature SCR at 80～160 and 200～350 °C, respectively. In addition, the available lattice oxygen was important for attaining high NO to NO₂ oxidation at low temperatures.

Implications: Recently, various Mn catalysts have been evaluated as SCR catalysts. However, there have been no studies on the relationship of adsorption and desorption properties and behavior of lattice oxygen according to the valence state for manganese oxides (MnO_x). Therefore, in this study, the catalysts were prepared by the wet-impregnation method at different calcination temperatures in order to show the difference of manganese oxidation state. These catalysts were then characterized using various physicochemical techniques, including BET, XRD, TPR, and TPD, to understand the structure, oxidation state, redox properties, and adsorption and desorption properties of the Mn/TiO₂ catalysts.     

TiO2纳米管的水热合成表征及其光催化性能研究

采用水热化学反应的方法制备了TiO2纳米管,并采用TEM、XRD等分析手段对TiO2纳米管的形貌和晶相进行了表征,对比了管与粉的光催化性能.结果表明,采用该方法制得的TiO2纳米管的管径小、管形均匀,TiO2纳米管的光催化性能明显高于TiO2纳米粉.     

制备方法对Mn-Ce/TiO2催化剂低温选择性催化还原活性的影响

采用溶胶凝胶法、浸渍法以及两者相结合的方法制备了Mn-Ce/TiO2催化剂。运用XRD、BET和SEM等技术对催化剂进行了表征,发现溶胶凝胶法制备的Mn-Ce/TiO2催化剂为锐钛矿结构,具有较大的比表面积,中孔结构丰富,Mn、Ce活性组分在载体表面高度分散或形成了无定形结构。实验研究了催化剂对氨选择性催化还原NO反应的催化性能,结果表明,用溶胶凝胶法制备的Mn-Ce/TiO2催化剂脱硝活性最好,当Mn、Ce负载量为20%,NH3/NO摩尔比为1.1,空速为9 436 h-1,烟气温度为240℃时,NO转化率大于90%。     

Synthesis of BiVO4/TiO2 composites and evaluation of their photocatalytic activity under indoor illumination

BiVO₄/TiO₂ composites with different weight ratios have been prepared by coprecipitation-based reactions followed by either thermal or hydrothermal treatment with the aim of evaluating the TiO₂ photosensitization by BiVO₄. The obtained materials present in all cases the desired monoclinic phase of BiVO₄ and anatase phase of TiO₂. Visible light absorption increased with increasing amount of bismuth vanadate. XPS results reveal the surface enrichment of Ti with respect to the bulk composition in samples characterised by a higher content of BiVO₄. The photocatalytic activity of the prepared materials was tested for the degradation of isopropanol in the gas phase under indoor illumination conditions. Although none of the composites was able to improve the activity of TiO₂, the low BiVO₄ containing samples appear as more suitable for further synthesis tuning.     

Mn的氧化价态对Mn／γ-Al2O3催化剂催化臭氧氧化气相低浓度甲苯的影响

采用共沉淀法,以Al2O3为载体制备Mn／γ-Al2O3和Mn—Ce／Mn／γ-Al2O3催化剂,并分别在N2气氛和O2气氛下焙烧。采用固定床连续流动反应器,研究所制备催化剂在室温条件下催化臭氧氧化甲苯的性能。通过XRD、XPS和FTIR等手段对催化剂的结构和组成进行表征。结果表明,Mn／Mn／γ-Al2O3催化剂具有良好的催化臭氧氧化甲苯和催化臭氧自身分解的性能,共沉淀法制备催化剂的最佳Mn负载量为20％。O2气氛焙烧和Ce的加入,可以有效提高催化剂的活性和寿命。原因是O2气氛焙烧和Ce的加入可以提高Mn的氧化价态。催化剂失活的主要原因是有机副产物在催化剂表面吸附堆积,失活催化剂在550℃、空气气氛下焙烧可恢复催化性能。     

Fe2O3-Cr2O3/TiO2系列催化剂的结构和脱硝性能

研究以纳米TiO2为载体,浸渍负载过渡金属氧化物,以CO为还原剂的脱硝催化剂的脱硝性能。实验中以计算量的Ni（NO3）2和Fe（NO3）3混合溶液浸渍纳米TiO2粉末,室温下搅拌30 min至混合均匀,放入旋转蒸发器中,70℃下至水分蒸干为止;所得粉末在550℃下、空气气氛中焙烧4 h即得所需催化剂。用以上方法分别制备2%Fe2O3-10%Cr2O3/TiO2、4%Fe2O3-8%Cr2O3/TiO2、6%Fe2O3-6%Cr2O3/TiO2、8%Fe2O3-4%Cr2O3/TiO2与10%Fe2O3-2%Cr2O3/TiO2等5种催化剂样品。实验结果表明,制备的催化剂具有较好的结构,分散较为均匀。对于CO＋NO反应,Fe2O3-Cr2O3/TiO2系列催化剂具有较好的催化活性,NO的转化率都达到了100%。其中,10%Fe2O3-2%Cr2O3/TiO2样品具有最好的低温活性,H2-TPR结果表明,这是由于10%Fe2O3-2%Cr2O3/TiO2催化剂更易于被CO预还原。     

纳米Bi2O3/TiO2复合光催化剂的制备及性能研究

以光催化效果为评价标准,采用超声波作用下水解法制备Bi2O3/TiO2复合光催化剂,考察了水解条件和Bi2O3掺入量等制备条件对复合光催化剂性能的影响。结果表明,与传统制备方法相比,该方法操作简单、快速;当水和乙醇的比例为4∶1时所得样品的光催化活性最好;Bi2O3的掺入拓宽了TiO2对光的吸收范围,提高了TiO2的光催化活性,掺入量(Bi2O3)为0.25%复合光催化剂催化活性最高;复合光催化剂对多种水溶性染料均具有较好的处理效果。     

Cu2O负载的TiO2纳米管阵列的光电催化活性及应用

通过方波伏安电化学沉积法成功制备了Cu2O负载的TiO2纳米管阵列（Cu2O/TNAs）异质结电极。利用FESEM、XRD、XPS、UV-vis对样品进行表征,研究其表面形态、晶型特征、化学组分和光学特性。通过电化学工作站测试、光电化学降解布洛芬同时产氢气的实验,研究Cu2O/TNAs电极的光电化学特性。FESEM结果表明Cu2O以花形和八面体结构负载在纳米管阵列上。XRD和XPS结果证明,样品中Cu元素以Cu2O形式存在。UV-vis表明Cu2O/TNAs的光响应范围红移至可见光区（Eg=2.19 eV）。光电化学测试结果表明所制备的Cu2O/TNAs异质结电极具有良好的光电化学性能,以100 W汞灯为光源,0.5 V外加电压条件下,电流达4.04 mA·cm-2。且电化学阻抗谱分析证明,负载Cu2O有利于抑制光生电子-空穴复合,有效延长电子寿命。在光电化学降解布洛芬同时产氢气的实验中,Cu2O/TNAs光电化学降解布洛芬和产氢气的效率明显优于TNAs。     

掺杂负载型纳米TiO2降解橙黄G的光催化活性及其动力学研究

采用溶胶-凝胶法和浸渍-焙烧法制备了掺杂Sn(Ⅳ)的TiO2/AC光催化剂,以偶氮染料橙黄G为目标降解物,对光催化反应条件进行了优化.结果表明:利用Sn(Ⅳ)掺杂量为2.5 at.%的TiO2/AC光催化剂,在进水浓度50 mg/L,催化剂的用量12.5 g/L,pH值2.0,H2O21.5 mL/L,主波长为365 nm的300W高压汞灯光照条件下,反应60 min,橙黄G的光催化去除率可达99.1%.该反应符合Langmuir-Hinshelwood动力学方程,其速控步为吸附反应.共存阴离子SO42-和H2PO4-,对橙黄G的光催化降解反应均有一定的抑制作用.     

参杂负载型纳米TiO2降解橙黄G的光催化活性及其动力学研究

采用溶胶-凝胶法和浸渍-焙烧法制备了掺杂Sn（Ⅳ）的TiO2／AC光催化剂，以偶氮染料橙黄G为目标降解物，对光催化反应条件进行了优化。结果表明：利用Sn（IV）掺杂量为2．5at．％的TiO2／AC光催化剂，在进水浓度50mg／L，催化剂的用量12．5g／i，pH值2．0，H2O2 1．5mL／L。主波长为365nm的300W高压汞灯光照条件下，反应60rain，橙黄G的光催化去除率可达99．1％。该反应符合Langmuir-Hinshelwood动力学方程，其速控步为吸附反应。共存阴离子SO4^2-和H2PO4^-，对橙黄G的光催化降解反应均有一定的抑制作用。     

CeOx对低温选择性催化还原脱硝催化剂FeOx-MnOx/TiO2的改性研究

制备了不同CeO_x负载量的(CeO_x)_n-(FeO_x)_(0.1)-(MnO_x)_(0.4)/TiO_2催化剂(n、0.1、0.4分别为CeO_x、FeO_x、MnO_x与载体TiO_2的摩尔比),用于低温选择性催化还原(SCR)脱硝,并对其进行结构和性能的表征。结果表明,适量负载CeO_x能够显著提高催化剂的低温SCR脱硝催化活性。当n=0.07时,催化剂在160～180℃时的催化活性最高,脱硝效率可以达到99%以上。同时,水蒸气、SO_2体积分数分别小于等于10%、0.02%时,该催化剂有较好的抗水性和抗硫性。表征结果显示,(CeO_x)_(0.07)-(FeO_x)_(0.1)-(MnO_x)_(0.4)/TiO_2催化剂锐钛矿TiO_2的相对结晶度低,耗氢还原峰温度低,并且面积大,表面Lewis酸位上的NH_3稳定。因此,(CeO_x)_(0.07)-(FeO_x)_(0.1)-(MnO_x)_(0.4)/TiO_2催化剂具有良好的低温SCR脱硝活性,并且稳定。     

Preparation of the Mn/Co mixed oxide catalysts for low-temperature CO oxidation reaction

The Mn/Co mixed powders with various Mn/Co molar ratios were prepared by the coprecipitation method and used in low-temperature CO oxidation. The physicochemical characteristics of these powders were characterized using the Brunauer-Emmett-Teller (BET), X-ray diffraction (XRD), temperature-programmed reduction (TPR), and scanning electron microscopy (SEM) analyses. The results demonstrated that the Mn/Co molar ratio significantly affected both the textural and catalytic properties and the sample with a Mn/Co = 1:1 possessed a BET area of 123.7 m²g⁻¹ with a small mean pore size of 6.44 nm. The catalytic results revealed that the pure cobalt and manganese catalysts possessed the low catalytic activity and the pure Co catalyst is not active at temperatures lower than 140 °C. The highest catalytic activity was observed for the catalyst with a Mn/Co = 1. The obtained results showed that the incorporation of Pd into the Mn/Co catalyst significantly enhanced the catalytic activity for oxidation of carbon monoxide and the highest CO conversion was observed for the catalyst with 1 wt.% Pd and this catalyst exhibited a CO conversion of 100% at 80 ^°C.

     

脉冲放电协同Ag改性Mn-TiO2/分子筛催化剂去除甲醛

为进一步提高Mn-TiO2/分子筛催化剂和等离子体协同的催化活性,增加CO2选择性,减少O3产量。以5A分子筛为催化剂载体,采用浸渍法并利用Ag改性制备了Ag-Mn-TiO2/分子筛催化剂,并运用XRD、SEM、EDS和FT-IR等技术对催化剂进行了表征。在针-板式高压脉冲反应器中研究了Ag的负载量与焙烧温度对Ag-Mn-TiO2/分子筛催化剂的催化活性、CO2选择性和O3的产量的影响。结果表明：掺杂Ag后,促进Mn价态向+4价转变,提高了Mn-TiO2/分子筛催化剂活性;焙烧温度为500℃时,Ag和Mn在分子筛上分布均匀,有利于Ag和Mn氧化物晶粒成长。当脉冲电压20 kV,Ag负载量为4%时,Ag-Mn-TiO2/分子筛催化剂的甲醛去除率达到97.6%,O3浓度为99.4 mg·m-3,CO2选择性为50.2%。     

Ce掺杂纳米TiO2光催化剂的制备及降解甲醛的研究

介绍了溶胶-凝胶法制备Ce离子掺杂纳米TiO2的工艺流程.采用X射线衍射(XRD)、紫外可见分光光度法(UV-Vis)等方法表征了Ce掺杂TiO2的相组成、紫外可见漫反射率与掺杂量的关系.结果表明,掺杂的TiO2在520℃、650℃焙烧2 h呈锐钛矿结构,在520℃焙烧2 h的TiO2的晶粒尺寸大约为20 nm,而掺杂Ce后其晶粒尺寸均减小,大约为12nm.UV-Vis吸光度分析表明,掺Ce后吸收带边明显发生红移,但随着Ce掺杂浓度的增大,其对可见光的吸收影响不大.光催化降解反应表明,未掺杂Ce的TiO2反应2 h后对甲醛的没有降解作用,而Ce掺杂TiO2反应2 h后甲醛降解率达15%.     

Ce掺杂纳米TiO2光催化剂的制备及降解甲醛的研究

介绍了溶胶-凝胶法制备Ce离子掺杂纳米TiO2的工艺流程。采用X射线衍射（XRD）、紫外可见分光光度法（UV-Vis）等方法表征了Ce掺杂TiO2的相组成、紫外可见漫反射率与掺杂量的关系。结果表明，掺杂的TiO2在520℃．650℃焙烧2h呈锐钛矿结构，在520℃焙烧2h的TiO2的晶粒尺寸大约为20nm，而掺杂Ce后其晶粒尺寸均减小，大约为12nm。UV-Vis吸光度分析表明，掺Ce后吸收带边明显发生红移，但随着Ce掺杂浓度的增大，其对可见光的吸收影响不大。光催化降解反应表明，未掺杂Ce的TiO2反应2h后对甲醛的没有降解作用，而Ce掺杂TiO2反应2h后甲醛降解率达15％。     

TiO2/H2O2/UV和TiO2/O3/UV降解对氯苯甲酸和喹啉的试验研究

主要叙述TiO2/H2O2/UV和TiO2/O3/UV体系降解对氯苯甲酸（4-CBA）和喹啉的试验研究.研究表明,（1）在TiO2/H2O2/UV体系里目标物降解速度先随过氧化氢投加量的增加而提高,但超过一定浓度之后便开始下降;（2）在TiO2/O3/UV体系中,目标降解物的反应速度都非常快,且臭氧浓度高的时候降解速度更快;（3）二氧化钛催化剂在TiO2/O3/UV体系中作为积极因素有助于提高反应速率,而在TiO2/H2O2/UV体系是消极因素,会降低反应速率.     

快速SCR反应对商用V2O5-WO3/TiO2催化剂脱硝特性的影响

通过实验考察了快速SCR反应对商用V2O5-WO3/TiO2催化剂脱硝特性的影响。在250～375 ℃的实验温度区间内,快速SCR反应能适应更宽的温度窗口而保持较高的效率;快速SCR反应在高空间速度（SV=12 400 h-1）的脱硝效率甚至要高于标准SCR反应在低空间速度（SV=7 400 h-1）时的脱硝效率;快速SCR反应在410～820 mg·m-3的NOx质量浓度内脱硝效率波动不大。通过快速SCR反应和标准SCR反应条件下的催化剂活性分析和体积量计算,快速SCR反应相较标准SCR反应可以提高活性1.4倍,减少催化剂用量28.57%,同时通过催化剂寿命计算,快速SCR反应可以延长现有SCR脱硝系统V2O5-WO3/TiO2催化剂寿命22 582 h,延长催化剂的更换周期941 d。