甲烷光催化氧化制甲醇研究进展

随着经济的发展，人们对能源的需求量日益增加．目前，世界上石油资源储量有限，而天然气是非常丰富的石油化工燃料资源，储量很大．现已探明的世界天然气储量为142．1万亿立方米，其能量相当于9143亿桶原油，远景储量为250～350万亿立方米．天然气资源与液体石油资源相比，其储量     

NOx气相光催化氧化降解研究

利用ＴｉＯ２光催化氧化技术对ＮＯｘ进行了净化研究,在一定反应条件下,ＮＯｘ光催化氧化降解率很高,Ｐ－２５的降解达９７％。考察了氧气,水含量等对ＮＯｘ光催化氧化的影响,同时对ＮＯｘ的吸附、光催化氧化动力学行为及机理进行了研究。利用ＦＴＩＲ分析确定反应产物,催化剂失活是由于反应产物硝酸吸附在催化剂表面所致。     

TiO2薄膜光催化气相甲醇制氢

 在气相连续流动装置中以TiO2薄膜为光催化剂，对甲醇的脱氢反应进行了研究．考察了空速、光照时间和反应温度对甲醇转化率的影响以及产氢量与添加的水蒸气量和甲醇浓度的关系，并将TiO2薄膜催化剂的光催化活性与TiO2纳米粉体催化剂进行了比较．反应动力学研究表明，光催化甲醇脱氢反应为一级反应，其活化能为8．64kJ／mol．探讨了该反应的机理．     

纳米二氧化钛气相光催化降解三氯乙烯

采用气相色谱－质谱联用方法,Ｘ射线光电子能谱和程序升温脱附方法研究了纳米二氧化钛表面三氯乙烯的气相光催化降解反应。检测到四种新的含三个碳原子的中间体,说明三氯乙烯在反应过程中发生了Ｃ＝Ｃ双键的裂解及加成反应。研究表明,水蒸气对降解反应的影响不公与水蒸气的浓度有关,还与催化剂对水的吸收能力有关。反应副产物在催化剂表面的积累是导致催化剂活性降低的主要原因。催化剂的Ｘ射线光电子能谱显示,反应后催化剂表面     

硅烷偶联剂改性的二氧化钛光催化降解气相苯

 用硅烷偶联剂KH-570对二氧化钛光催化剂进行了改性,制备了一种新型光催化剂. 以苯作为 模拟气体,在静态反应装置中考察了该催化剂的光催化性能. 结果表明,KH-570能显著提高 二氧化钛对气相苯的光催化降解性能,其转化率是纯二氧化钛的2.5倍. 采用红外光谱和X射线光电子能谱对催化剂进行了表征.     

甲醇阳极电氧化催化剂的研究

采用化学还原沉积法制备了Ｐｔ－ＷＯ３／Ｃ，Ｐｔ－Ｒｕ／Ｃ和Ｐｔ－ＷＯ３／Ｃ系列催化剂，通过循环伏安与电流－电位极化研究了甲醇在不同催化剂／Ｎａｆｉｏｎ奄极上的电催化氧化。结果表明，三种催化剂的催化活性顺序为：Ｐｔ－Ｒｕ－ＷＯ３／Ｃ〉Ｐｔ－Ｒｕ／Ｃ〉Ｐｔ－ＷＯ３／Ｃ。同时研究了甲醇浓度和催化剂的配比对阳极性能的影响。     

对苯二胺衍生物的光催化氧化

以ＴｉＯ２作为催化剂，利用波长＞３３０ｎｍ的光辐照研究了Ｎ－取代的对苯－二胺衍生物的光催化氧化。研究表明，氧分子与光生电子 反应生成羟基自由基，羟基自由基氧化ＰＰＤｓ，生成醌二亚胺，后者在羟基的进攻下脱氨生成苯醌，苯醌继续光解无机化。ＰＰＤｓ光催化氧化近似遵循一级反应动力学，醇类和硫酸根离子可抑制ＰＰＤｓ的光催化氧化。催化剂表面荷影响电子转移速率，从而控制光催化氧化的反应速率。     

铂催化甲醇氧化开始步骤的研究

用ab initio和密度泛函(DFT)方法研究甲醇在铂低指数晶面的脱氢步骤. 在经典的Bagotzky模型计算的基础上提出了三种新的吸附脱氢模型, 并通过计算证明了三种模型的可行性, 计算证实了原位波谱法检测到的甲醇在铂上脱氢的三种中间体, CHOH, CH₂OH和CH₃O. 得出了甲醇脱氢的根本原因在于形成的强Pt—H键, 且在Pt不同的晶面上, 催化性能及反应历程、中间产物都不同.     

甲醇气相氧化羰基化合成碳酸二甲酯的研究

制备了甲醇气相氧化羰基化催化合成碳酸二甲酯催化剂，在常压固定床反应装置上评价了其反应性能，考察了且剂和载体的影响。结果表明：负载在活性炭载体上的单一金属氯化物催化剂的活性相当低，而双金属氯化物催化剂ＰｄＣｌ２－ＣｕＣｌ２／ＡＣ可明显提高碳酸二甲酯的产率。不同的活性炭载体显著地反应活性。碱性助剂Ｋ、Ｍｇ能大幅度增加碳酸二甲酯的时空收率和对ＣＯ的选择性，但必需以乙酸的形式加入，ＰｄＣｌ－ＣｕＣｌ２－Ｃ     

TiO2气相光催化氧化降解三氯乙烯的产物分布及失活机理研究

用ＧＣ／ＭＳ、ＴＰＤ和ＸＰＳ方法,研究了三氯乙烯的气相光催化降解反应,检测到新的中间体乙二酰氯（ＣＩＣＯＣＯＣＩ）。对产物分布的分析表明,水蒸汽的存在能显著抑制含氯副产物的生成,改变反应产物的分布。使用过的催化剂的ＸＰＳ谱图显示,催化剂表面存在含氯副产物,反应副产物在催化剂表面的积累是导致催化剂失活的主要原因。     

Recent Advances in Photocatalytic Oxidation of Methane to Methanol

Methane is one of the promising alternatives to non-renewable petroleum resources since it can be transformed into added-value hydrocarbon feedstocks through suitable reactions. The conversion of methane to methanol with a higher chemical value has recently attracted much attention. The selective oxidation of methane to methanol is often considered a “holy grail” reaction in catalysis. However, methanol production through the thermal catalytic process is thermodynamically and economically unfavorable due to its high energy consumption, low catalyst stability, and complex reactor maintenance. Photocatalytic technology offers great potential to carry out unfavorable reactions under mild conditions. Many in-depth studies have been carried out on the photocatalytic conversion of methane to methanol. This review will comprehensively provide recent progress in the photocatalytic oxidation of methane to methanol based on materials and engineering perspectives. Several aspects are considered, such as the type of semiconductor-based photocatalyst (tungsten, titania, zinc, etc.), structure modification of photocatalyst (doping, heterojunction, surface modification, crystal facet re-arrangement, and electron scavenger), factors affecting the reaction process (physiochemical characteristic of photocatalyst, operational condition, and reactor configuration), and briefly proposed reaction mechanism. Analysis of existing challenges and recommendations for the future development of photocatalytic technology for methane to methanol conversion is also highlighted.     

纳米Pt/TiO2催化剂上气相CH3OH光催化分解制氢反应的研究

利用不同还原方法制备了不同纳米粒度的Pt/tiO2光催化剂,并且用脉冲氢氧滴定法测定了TiO2表面Pt的分散度.在气相连续流动装置中利用纳米Pt/tiO2作为光催化剂,对气相甲醇的脱氢反应进行了研究.研究了添加Pt和不添加Pt的纳米TiO2,Pt负载量、铂的不同还原方法、不同TiO2纳米粒度对气相甲醇光催化分解反应的影响,并对反应气的空速、光照时间、添加水蒸汽、改变甲醇浓度等与光催化分解甲醇制氢的关系进行了研究,在最佳反应条件下,产氢速率达到5.808 mmol/(g·h).研究了反应的动力学,得到该反应为一级反应,求得了该反应的活化能为8.53 kJ/mol,并讨论了反应机理.     

羟基化氧化锌催化甲醇裂解反应机理的理论研究

采用密度泛函理论的B3LYP方法在两种基组水平上研究了羟基化氧化锌催化裂解甲醇反应机理, 优化了反应过程中各反应物、中间体、过渡态和产物几何构型, 并且应用了自然轨道理论(NBO)和分子中的原子理论(AIM)分析了这些物质的成键特征和轨道间的相互作用. 研究中分别采用了羟基化一个ZnO和羟基化两个ZnO作为催化剂的两种简化模型. 结果表明两种不同基组研究所得的反应历程及相应能量变化趋势一致; 羟基化两个ZnO催化剂活化裂解甲醇反应更容易发生.     

掺铁TiO2气相光催化降解正己烷的研究

利用钛酸丁酯水解浸渍、共沉淀、水热等方法制备了掺铁TiO2纳米复合粉体材料并通过XRD、BET、TEM等手段作了表征，研究了掺铁TiO2对气相光催化降解正己烷反应的活性并和商品TiO2 Degussa P-25作了比较，考察了制法、掺铁量、焙烧温度等的影响。结果表明，和大多数液相反应不同，铁的掺入抑制了TiO2对正己烷的气相光催化降解。水热处理能较大程度地改善掺铁和未掺铁TiO2的光催化性能。P-25对正己烷的气相光催化活性则明显小于未掺铁TiO2样品，也小于某些掺铁样品。     

Experimental Identification of Ultrafast Reverse Hole Transfer at the Interface of the Photoexcited Methanol/Graphitic Carbon Nitride System

An experimental scrutiny of the photoexcited hole dynamics in a prototypical system is presented in which hole‐scavenging methanol molecules are chemisorbed on a graphitic carbon nitride (g‐C₃N₄) substrate. A set of comparison and control experiments by means of femtosecond time‐resolved transient absorption (fs‐TA) spectroscopy were conducted. The elusive reverse hole transfer (RHT) process was identified, which occurs on a timescale of a few hundred picoseconds. The critical role of interfacially chemisorbed methoxy (instead of methanol) as the dominant species responsible for hole scavenging was confirmed by a control experiment using protonated g‐C₃N₄ as the substrate. A hot‐hole transfer effect was revealed by implementing different interband photoexcitation scenarios. The RHT rate is the key factor governing the hole‐scavenging ability of different hole scavengers.     

甲醇催化分解研究进展

出于对环境和能源的双重考虑,甲醇催化分解过程越来越受到重视。研究者们进行了大量的研究并取得了显著的进展。本文简要概括该催化过程的研究和进展、存在问题及其发展方向。参考文献56篇。     

Study of the Efficiency of UV and Visible‐Light Photocatalytic Oxidation of Methanol on Mesoporous RuO2–TiO2 Nanocomposites

Mesoporous RuO₂–TiO₂ nanocomposites at different RuO₂ concentrations (0–10 wt %) are prepared through a simple one‐step sol–gel reaction of tetrabutyl orthotitanate with ruthenium(III) acetylacetonate in the presence of an F127 triblock copolymer as structure‐directing agent. The thus‐formed RuO₂–TiO₂ network gels are calcined at 450 °C for 4 h leading to mesoporous RuO₂–TiO₂ nanocomposites. The photocatalytic CH₃OH oxidation to HCHO is chosen as the test reaction to examine the photocatalytic activity of the mesoporous RuO₂–TiO₂ nanocomposites under UV and visible light. The photooxidation of CH₃OH is substantially affected by the loading amount and the degree of dispersion of RuO₂ particles onto the TiO₂, which indicates the exclusive effect of the RuO₂ nanoparticles on this photocatalytic reaction under visible light. The measured photonic efficiency ξ=0.53 % of 0.5 wt % RuO₂–TiO₂ nanocomposite for CH₃OH oxidation is maximal and the further increase of RuO₂ loading up to 10 wt % gradually decreases this value. The cause of the visible‐light photocatalytic behavior is the incorporation of small amounts of Ru⁴⁺ into the anatase lattice. On the other hand, under UV light, undoped TiO₂ shows a very good photonic efficiency, which is more than three times that for commercial photocatalyst, P‐25 (Evonik–Degussa); however, addition of RuO₂ suppresses the photonic efficiency of TiO₂. The proposed reaction mechanism based on the observed behavior of RuO₂–TiO₂ photocatalysts under UV and visible light is explored.     

Photocatalytic Reaction of Sulfur Dioxide with Heptane in the Gas-phase Over Titanium Dioxide

IntroductionA broad range of orgainc compounds[1 ,2 ]can be oxidized by means of semiconductor pho-tocatalysis with a primary focus on Ti O2 as a durable photocatalyst in recent years.WhenTi O2 is illuminated with the light of energy greater than the semiconductor band gap,elec-tron- hole pairs(e-- h ) are formed in the conduction and thevalence bandsof thesemiconduc-tor,respectively.These charge carriers,which migrate to the semiconductor surface,are ca-pable of activating oxygen species,et…