催化基底表面亲水改性对氢气催化氧化效率影响的密度泛函研究

催化剂表面亲疏水性改性是一种常见的调控手段,其对催化剂催化活性、选择性和稳定性有着重要的影响。以氢气催化氧化转化为水为研究对象,从分子水平出发,通过多尺度密度泛函理论(DFT)计算了催化剂在不同程度的表面亲水改性后对水和氢气的吸附作用,并研究了吸附对于反应效率的影响。结果表明,随着表面亲水性的增强,催化剂表面对水吸附越来越多,而受体积排斥效应影响,氢气的吸附量越来越少。而对于同一催化剂表面,增大水分子的均相密度量可促进氢气在表面的吸附。该理论结果不仅很好地解释了催化剂表面亲水性对于催化活性的影响,且为表界面反应的效率调控与强化提供了思路。     

DOP液相催化加氢制DEHCH及其动力学研究

以邻苯二甲酸二异辛酯(DOP)为原料,考察了4种金属催化剂作用下加氢制取环己烷二甲酸二异辛酯(DEHCH)的催化效果,系统研究了反应温度、氢气压力、反应时间和催化剂用量的影响。结果表明,Rh/C的催化活性最高;反应温度对加氢反应速度的影响较小,而氢气压力和催化剂用量的影响比较显著。实验确定了DOP加氢的适宜工艺条件为:温度为170℃,氢气压力2.0 MPa,反应时间为4.0 h。在此条件下,DEHCH是反应的唯一产物,收率高达99.5%以上。DOP加氢的表观动力学分析表明,催化剂表面上的吸附氢气浓度是加氢过程的控制步骤。     

助催化剂对甲苯歧化与烷基转移催化剂性能的影响

采用助催化剂对丝光沸石进行改性,通过红外光谱（FT—IR）方法表征了该改性分子筛制备的催化剂样品表面酸性的变化,并探讨了酸性变化对甲苯歧化与烷基转移反应催化活性的影响。结果表明,助催化剂WO3的加入能有效地调节催化剂表面酸性,经氢气还原后催化剂B酸量随助催化剂量增加而增加,且与助催化剂相对含量呈对数关系;而L酸量随助催化剂相对含量的增加先上升,随后趋于平稳;催化剂的反应活性随助催化剂含量的增加而增加,但副反应也随之加大。     

二氧化钛改性α-氧化铝载体对银催化剂催化乙烯环氧化反应性能的影响

为了排除载体孔结构变化对催化性能的影响,研究了二氧化钛改性α-氧化铝载体对银催化剂催化乙烯环氧化反应性能的影响。研究结果表明,二氧化钛表面改性α-氧化铝载体对载体的比表面积、孔结构无明显影响;载体表面改性导致催化活性组分银在载体表面均匀分散,分散状况明显改善;经二氧化钛改性后载体表面与银的相互作用增强;对单负载银催化剂,由改性载体制备的银催化剂的活性和选择性均下降,改性对催化性能明显不利;对于共浸渍法制备的多组分银催化剂,低温焙烧对催化性能不利,而由经1000℃高温焙烧的二氧化钛改性载体制备的银催化剂的催化活性明显提高。研究表明,载体表面等电点降低及其与银的强相互作用是造成催化剂上金属银良好分散的主要原因;此外,银催化剂助剂的存在减弱了二氧化钛改性载体与银之间的强相互作用、抑制了环氧乙烷（EO）深度反应的活性,两者协同作用提升了多组分银催化剂的催化反应性能。     

二氧化钛改性α-氧化铝载体对银催化剂催化乙烯环氧化反应性能的影响

为了排除载体孔结构变化对催化性能的影响,研究了二氧化钛改性α-氧化铝载体对银催化剂催化乙烯环氧化反应性能的影响。研究结果表明,二氧化钛表面改性α-氧化铝载体对载体的比表面积、孔结构无明显影响;载体表面改性导致催化活性组分银在载体表面均匀分散,分散状况明显改善;经二氧化钛改性后载体表面与银的相互作用增强;对单负载银催化剂,由改性载体制备的银催化剂的活性和选择性均下降,改性对催化性能明显不利;对于共浸渍法制备的多组分银催化剂,低温焙烧对催化性能不利,而由经1000℃高温焙烧的二氧化钛改性载体制备的银催化剂的催化活性明显提高。研究表明,载体表面等电点降低及其与银的强相互作用是造成催化剂上金属银良好分散的主要原因;此外,银催化剂助剂的存在减弱了二氧化钛改性载体与银之间的强相互作用、抑制了环氧乙烷(EO)深度反应的活性,两者协同作用提升了多组分银催化剂的催化反应性能。     

表/界面调控策略在氢/氧反应电极中的研究进展

高效的非贵金属基电催化剂对于提升氢气析出反应（HER）、氧气析出反应（OER）、氧气还原反应（ORR）等电催化反应的整体效率、促进能源转换技术的发展及应用起着至关重要的作用。近年来,对现有的电催化剂进行表/界面调控以诱导其产生新的理化性质,从而提高催化活性的研究受到了广泛的关注。本文综述了近年来利用形貌尺寸调控、缺陷调控、杂原子掺杂、异质结结构等表/界面调控策略在设计非贵金属基电催化剂方面的研究进展,揭示了催化材料体系改性对优化和提升催化性能的关键特性。从催化剂制备、先进表征手段、理论计算、应用性评价等方面展望了非贵金属基电催化剂在实际应用中存在的挑战和未来的研究方向,为实现清洁能源的大规模应用提供参考。     

硫化La1-xSrxCoO3的电性能和CO催化还原SO2性能

对催化剂La1-xSrxCoO3(x=0.0~0.3)硫化后的结构、电性能和CO还原SO2的活性进行了研究。结果表明,硫化La1-xSrxCoO3为P型导体,在反应气氛下结构为La0.8Sr0.2CoO3催化剂对SO2的吸附量较大,其催化活性较高,而La0.7Sr0.3CoO3对SO2的吸附量较小,催化活性也相对较低,催化剂对SO2的吸附量与催化活性存在对应的关系。     

不同金属助剂对HZSM-5分子筛催化分解甲硫醇性能的影响

采用浸渍的方式制备不同系列金属（Cr、La和Na）改性HZSM-5催化剂,并研究其对甲硫醇催化分解活性的影响以及分析相关性能差异的原因。通过XRD、BET、SEM、NH₃-TPD、CO₂-TPD、H₂-TPR和XPS等表征手段对催化剂的物化性质进行测定,结果表明：不同系列金属改性HZSM-5对甲硫醇表现出不同的催化活性及影响效果,其中Cr和La改性HZSM-5能明显提高催化剂的催化活性,在500℃下可实现甲硫醇的完全催化转化,这主要归因于Cr的引入提高了催化剂的氧化还原能力,从而促进甲硫醇的催化分解;La的引入增加了催化剂表面的碱性位点,有利于甲硫醇在催化剂表面的吸附和活化。而Na改性HZSM-5表现出较差的催化活性,主要是由于过多Na的添加严重破坏了HZSM-5的骨架结构,从而导致催化剂的催化稳定性能降低。     

锰改性磁铁矿催化NH_3-SCR脱硝性能研究

采用水热法制备锰改性磁铁矿型催化剂用于烧结烟气选择性催化还原脱硝反应,研究水热反应温度对催化剂物理化学性能及脱硝性能的影响。结果表明,160℃水热反应制备的催化剂MnFe_2O_4-160表现出最佳的脱硝性能,在反应温度80℃即可达到90%的脱硝效率。提高锰的平均价态,促进表面吸附氧含量,增大比表面积,有利于提高锰改性磁铁矿催化剂的低温脱硝性能。     

催化剂表面硅烷化改性对甲醇合成反应的影响

为了减少甲醇合成催化剂(CuO/ZnO/Al_2O_3)载体Al_2O_3表面羟基与甲醇羟基形成氢键发生吸附,用γ-(甲基丙烯酰氧)丙基三甲氧基硅烷偶联剂对催化剂进行改性,并用FTIR,SEM对改性催化剂的结构特征和形貌进行表征评价。结果表明:Al_2O_3表面羟基与硅烷偶联剂发生缩合反应,实现了催化剂表面羟基的修饰改性;未经改性的氧化铝单体之间发生明显的团聚,而改性氧化铝颗粒之间聚集效应减弱;改性催化剂对甲醇、异丙醇和仲丁醇的吸附量明显少于未改性催化剂的吸附量。在固定床中考察催化剂改性对甲醇合成反应的影响,发现异丙醇和仲丁醇溶剂中改性催化剂的甲醇生成速率明显比未改性催化剂的甲醇生成速率快,气相甲醇条件下改性催化剂的甲醇合成速率是未改性催化剂的1.2倍。     

钌基氨合成催化剂氢氮吸附性能的研究

The effects of promoters K, Ba, Sm on the chemisorption and desorption of hydrogen and nitrogen, dispersion of metallic Ru and catalytic activity of active carbon (AC) supported ruthenium catalyst for ammonia synthesis have been studied by means of pulse chromatography, temperature-programmed desorption, and activity test. Promoters K, Ba and Sm increased the activity of Ru/AC catalysts for ammonia synthesis significantly, and particularly, potassium exhibited the best promotion on the activity because of the strong electronic donation to metallic Ru. Much higher activity can be obtained for Ru/AC catalyst with binary or triple promoters. The activity of Ru/AC catalyst is dependent on the adsorption of hydrogen and nitrogen. The high activity of catalyst could be ascribed to strong dissociation of nitrogen on the catalyst surface. Strong adsorption of hydrogen would inhibit the adsorption of nitrogen, resulted in decrease of the catalytic activity. Ru/AC catalyst promoted by Sm2O3 shows the best dispers     

非晶态Ni-P合金上硝基苯催化加氢制苯胺的本征动力学

Ni-P非晶态合金催化剂因其晶体结构的特殊,具有较好的催化活性。以硝基苯液相催化加氢合成苯胺为目标反应,运用Matlab软件并借助Levenberg-Marquardt算法估计反应动力学模型的参数,根据参数估计结果筛选动力学机理模型,对新型Ni-P非晶态合金催化剂的本征动力学进行研究,为催化剂的进一步开发和反应器设计提供理论依据。结果表明,Ni-P非晶态合金催化剂的颗粒较小,过程内扩散的影响可以忽略不计,当搅拌速率达到600 r·min^-1时,反应过程的外扩散影响也可忽略。在（373.15~403.15） K、氢压1.0 MPa、非晶态Ni-P催化剂质量0.2 g、硝基苯质量2.0 g和无水乙醇质量8.0 g条件下,硝基苯分子不吸附,硝基苯分子与解离吸附的氢原子在催化剂表面反应,苯胺脱附为硝基苯加氢合成苯胺反应的速率控制步骤,本征动力学模型为：r_j=kc_A/1+b_H2α_H2p_H2,表面反应的指前因子为1.08×105 min^-1,活化能为51.81 kJ·mol-1,氢气吸附热为64.12 kJ·mol^-1。     

The effect of copper valence on catalytic combustion of styrene over the copper based catalysts in the absence and presence of water vapor☆

Catalysts Cu Ox/γ-Al_2O_3-IH and Cu Ox/γ-Al_2O_3-IM were prepared, characterized, and tested for styrene combustion in the absence and presence of water vapor. The effect of copper valence of the catalysts on the catalytic activity for styrene combustion was discussed using the theory of hard soft acids and bases(HSAB).The results showed that the existence of water vapor in feed stream inhibited the catalytic activity for styrene combustion due to the competition adsorption of water molecule. HSAB theory confirmed that the local soft acidity of the catalyst Cu Ox/γ-Al_2O_3-IH was much stronger than that of the catalyst Cu Ox/γ-Al_2O_3-IM because of the higher content of soft acid Cu+on its surface, which increased the adsorption ability toward soft base of styrene and reduced the adsorption toward hard base of water vapor, and thus increased the catalytic activity for styrene combustion and weakened the negative influence of water vapor.     

Adsorption and reduction of nitrate in water on hydrotalcite-supported Pd-Cu catalyst

The hydrotalcite-supported Pd-Cu catalysts were successfully prepared by the impregnation or coprecipitation method, and their adsorption and catalytic reduction activity for nitrate in water were evaluated. The catalysts were characterized by X-ray diffraction (XRD) and surface area (BET) analysis. The results demonstrated that hydrotalcite-supported Pd-Cu catalysts could significantly adsorb nitrate ions, and then, effectively catalytically reduce them. The excellent adsorption ability for nitrate resulted from the regenerated layer structure of calcined hydrotalcite catalyst in nitrate aqueous solution. Nitrate was forced into the interlayer space and adsorbed on the external surface. The adsorption kinetics and the adsorption isotherm could be well described by pseudo-second-order model and the Langmuir model, respectively. The comparison of catalytic reduction with the adsorption for nitrate indicated that catalytic hydrogenation activity for nitrate increased with increasing adsorption capacity; nitrate reduction on hydrotalcite-supported Pd-Cu catalysts was a consecutive and dynamic adsorption and catalytic hydrogenation process. In addition, the catalyst obtained by coprecipitation method, with intact regeneration of hydrotalcite structure and a high dispersion of active metals, hold higher adsorption and catalytic activity than that prepared by co-impregnation method.     

MnO x -ZSM-5脱硝催化剂制备的溶剂效应研究

MnO _x -ZSM-5脱硝催化剂具有较好的低温氨选择性催化还原反应（NH₃-SCR）活性,因其原料成本低、脱硝效率高等优点成为研究热点。详细叙述了采用蒸干溶剂法、通过调变制备过程中溶剂组成（乙醇和水或其混合溶液）制备系列MnO _x -ZSM-5催化剂,并首次研究了“溶剂效应”对催化剂脱硝性能产生影响的原因。利用X射线衍射（XRD）、光电子能谱仪（XPS）、程序升温氨吸附法（NH₃-TPD）、N₂物理吸附、氢气程序升温还原（H₂-TPR）以及扫描电子显微镜（SEM）等表征手段分析了催化剂物化性质、锰存在状态与催化性能之间的相互关系。结果发现,随着溶剂中水分占比的提高,MnO _x -ZSM-5脱硝催化剂的比表面积降低,具有高催化活性的Mn⁴⁺物种比例迅速下降,这些原因均导致催化剂的脱硝活性逐步降低。说明溶剂组成会影响催化剂的脱硝性能,因此在制备MnO _x -ZSM-5脱硝催化剂时选取合适的溶剂是至关重要的,这为如何制备高活性的MnO _x -ZSM-5脱硝催化剂提供了重要信息。     

硝酸胶溶剂对CuO/HZSM-5成型催化剂性能的影响

催化剂CuO/HZSM-5在氧化亚氮(N₂O)催化分解领域有着重要地位,完成对催化剂成型条件的探索是其工业实际应用的重要步骤。在CuO/HZSM-5成型过程中,胶溶剂的用量对成型催化剂的机械强度,催化活性以及其他物化性质有重要的影响。通过机械强度测定、活性评价、X射线衍射分析(XRD)、孔结构分析、氨气程序升温吸附脱附分析(NH₃-TPD)、氢气程序升温还原分析(H₂-TPR)等手段对催化剂性能进行分析。机械强度测定与NH₃-TPD分析结果显示,胶溶剂用量对成型催化剂机械强度和酸量影响较大,胶溶剂用量为体积分数2%时,机械强度最高为135.8 N·cm^-1,而催化剂酸量在胶溶剂用量为体积分数7%时最高。XRD与孔结构分析结果显示胶溶剂用量由0增长至体积分数7%,催化剂的孔容积改变幅度较小,但比表面积由277 cm²·g^-1增至293 cm²·g^-1,HZSM-5的特征峰变化较小。活性评价与H₂-TPR分析结果显示,胶溶剂用量为0的催化剂与添加胶溶剂后的成型催化剂,N₂O完全分解的温度提高幅度最大为20 ℃,活性下降,且H₂-TPR中还原峰提高幅度最大为27 ℃,可还原性变差。而胶溶剂用量由体积分数2%提高至7%,成型催化剂CuO/HZSM-5的催化活性以及可还原性差异较小。     

磁性水滑石负载纳米钯催化剂的制备及催化Suzuki反应的研究

采用化学沉淀法将磁性基质与二维层状水滑石组装制备了磁性的水滑石,再利用浸渍法和滴加吸附的负载方法制备了磁性水滑石负载纳米钯催化剂。通过XRD、ICP—AES、TG、氢气脉冲吸附等分析手段对磁性催化剂晶型结构、形貌及金属分散度进行了表征,考察了用磁性水滑石负载纳米钯催化剂对不同碱、溶剂、溶剂与水比例、时间、温度、催化剂用量等条件对Suzuki反应的影响。实验结果表明,水滑石赋予磁性后结构并没有改变,仍然具有较高的催化活性。反应的最佳条件为：碳酸钾作碱、溶剂为乙醇、与水比例为1：5、反应温度为60℃、反应1h、催化剂用量分别为3．6×10^-3mmol和4．8×10^-3mmol,催化剂重复三次产物收率仍可保持在90％以上。     

Kinetics of isotopic exchange reaction between hydrogen and water vapor over platinum supported on a hydrophobic carrier

The isotopic exchange reaction between hydrogen and water vapor was studied for the temperature range 313 K to 353 K over platinum supported on hydrophobic styrene-divinylbenzene copolymer beads, and, for comparison, platinum supported on hydrophilic alumina pellets. The hydrophobic catalyst exhibited a high activity even with the gas saturated with water vapor, whereas the hydrophilic catalyst showed maximum exchange rate at a relative humidity of approximately 0.6. The dependences of the exchange rates on relative humidity, hydrogen partial pressure and temperature were extensively examined. The combined effect of surface reaction and intraparticle diffusion on the overall exchange reaction was analyzed to explain the kinetic behavior on the hydrophobic catalyst.     

Inhibiting and deactivating effects of water on the selective catalytic reduction of nitric oxide with ammonia over MnOx/Al2O3

The effect of water on the selective catalytic reduction (SCR) of nitric oxide with ammonia over alumina supported with 2–15 wt.-% manganese oxide was investigated in the temperature range 385–600 K, with the emphasis on the low side of this temperature window. Studies on the effect of 1–5 vol.-% water vapour on the SCR reaction rate and selectivity were combined with TPD experiments to reveal the influence of water on the adsorption of the single SCR reactants. It turned out that the activity decrease due to water addition can be divided into a reversible inhibition and an irreversible deactivation. Inhibition is caused by molecular adsorption of water. TPD studies showed that water can adsorb competitively with both ammonia and nitric oxide. Additional kinetic experiments revealed that adsorbed ammonia is present in excess on the catalyst surface, even in the presence of water. Reduced nitric oxide adsorption is responsible for the observed reversible decrease in the reaction rate; the fractional reaction order changes from 0.79 in the absence of water to 1.07 in its presence. Deactivation is probably due to the dissociative adsorption of water, resulting in the formation of additional surface hydroxyls. As the amount of surface hydroxyls formed is limited to a saturation level, the deactivating effect on the catalyst is limited too. The additional hydroxyls condense and desorb in the temperature range 525–775 K, resulting in a lower degree of deactivation at higher temperature. A high temperature treatment at 775 K results in a complete regeneration. The amount of surface hydroxyls formed per unit surface area decreases at increasing MnO_x-loading. The selectivity to the production of nitrogen is enhanced significantly by the presence of gas phase water.     

器外预硫化催化剂加氢脱酸性能研究

为探索器内硫化与器外预硫化催化剂的催化活性,采用等体积浸渍法制备同一批次镍-钨氧化态催化剂,分别采用器内硫化与器外预硫化得到3种不同的催化剂,考察3种新鲜催化剂的物化性质、催化活性和使用后催化剂的物化性质。结果表明：随着催化剂上硫化物负载量增加,预硫化催化剂的表观密度增加,比表面积、孔容、平均孔径均降低,同时预硫化催化剂在各个孔径范围内的分布均降低;3种催化剂中高负载硫的器外预硫化催化剂上W ⁴⁺态金属和NiWS活性相原子分数最高,器内硫化催化剂次之,低负载硫的器外预硫化催化剂最低;在反应压力为3.0 MPa、空速为1.0 h ^-1、氢油体积比为400∶1条件下,以绥中常二线、减三线馏分油为原料在不同反应温度下评价催化剂的活性,高负载硫的器外预硫化催化剂的脱酸、脱硫、脱氮活性最高,器内硫化催化剂次之,低负载硫的器外预硫化催化剂的催化活性最差。