高分散Ru/Si_(3)N_(4)催化剂的制备及其在CO_(2)加氢中的应用

氮化硅是一种良好的载体,具有较高的水热稳定性和机械稳定性,其表面的氨基基团能够较好地锚定金属,显著提高金属分散度。但是,商品氮化硅比表面积较低,对金属分散作用仍然有限。因此,以自制的高比表面积氮化硅(Si_(3)N_(4))为载体,通过浸渍法制备了不同Ru负载量(质量分数分别为0.5%、1.0%和2.0%)的催化剂(分别为0.5%Ru/Si_(3)N_(4)、1.0%Ru/Si_(3)N_(4)和2.0%Ru/Si_(3)N_(4)),并以商品氮化硅(Si_(3)N_(4)-C)为载体制备了2.0%Ru/Si_(3)N_(4)-C催化剂作为对照组。表征了催化剂的理化性质,测试了其在300℃、0.1 MPa下的CO_(2)加氢反应活性。结果显示,与Si_(3)N_(4)-C相比,Si_(3)N_(4)的比表面积较高(502 m^(2)/g),Si_(3)N_(4)作为载体显著提高了金属分散度,降低了金属粒径,催化剂暴露出更多的活性位点。0.5%Ru/Si_(3)N_(4)的金属粒径较小,展现出强的H_(2)吸附能力,H难以解吸,抑制了中间物种CO加氢生成CH_(4)。随着Ru负载量增加,金属粒径增大,催化剂的CH_(4)选择性更好。Ru/Si_(3)N_(4)系列催化剂中,2.0%Ru/Si_(3)N_(4)的CH_(4)选择性较高(98.8%)。空速为10000 m L/(g·h)时,0.5%Ru/Si_(3)N_(4)的CO选择性为88.2%。与2.0%Ru/Si_(3)N_(4)相比,2.0%Ru/Si_(3)N_(4)-C的金属粒径更大,活性位点较少,活性更低。2.0%Ru/Si_(3)N_(4)和2.0%Ru/Si_(3)N_(4)-C的CO_(2)转化率分别为53.1%和9.2%。Si_(3)N_(4)有效提高了金属分散度,提高了催化剂的CO_(2)加氢反应活性;通过调控Ru负载量控制催化剂金属粒径,可实现对产物CO或CH_(4)选择性的调控。

Polygonal mesopores microflower catalysts for the catalytic oxidation of 2-nitro-4-methylsulfonyltoluene to 2-nitro-4-methylsulfonylbenzoic acid in a continuous-flow microreactor

The development of efficient systems for the catalytic oxidation of 2-nitro-4-methylsulfonyltoluene(NMST)to 2-nitro-4-methylsulfonyl benzoic acid(NMSBA)with atmospheric air or molecular oxygen in alkaline medium presents a significant challenge for the chemical industry.Here,we report the synthesis of FeOOH/Fe_(3)O_(4)/metal-organic framework(MOF)polygonal mesopores microflower templated from a MIL-88B(Fe)at room temperature,which exposes polygonal mesopores with atomistic edge steps and lattice defects.The obtained FeOOH/Fe_(3)O_(4)/MOF catalyst was adsorbed onto glass beads and then introduced into the microchannel reactor.In the alkaline environment,oxygen was used as oxidant to catalyze the oxidation of NMST to NMSBA,showing impressive performance.This sustainable system utilizes oxygen as a clean oxidant in an inexpensive and environmentally friendly NaOH/methanol mixture.The position and type of substituent critically affect the products.Additionally,this sustainable protocol enabled gram-scale preparation of carboxylic acid and benzyl alcohol derivatives with high chemoselectivities.Finally,the reactions can be conducted in a pressure reactor,which can conserve oxygen and prevent solvent loss.Moreover,compared with the traditional batch reactor,the self-built microchannel reactor can accelerate the reaction rate,shorten the reaction time,and enhance the selectivity of catalytic oxidation reactions.This approach contributes to environmental protection and holds potential for industrial applications.

Al_(2)O_(3)在储能材料中的应用研究进展

Al_(2)O_(3)作为陶瓷材料、催化剂、催化剂载体及研磨磨料等有广泛的应用。因氧化铝具有优良的抗酸碱腐蚀性和力学等性能且热稳定性好、来源丰富,所以近年来逐渐开始应用在储能材料领域,进一步拓展了氧化铝的应用范围。主要针对氧化铝包覆后的二次储能电池正极材料、负极材料,以及改进隔膜的力学性能等方面进行研究。报道了近年来氧化铝在锂离子电池、钠离子电池、锂硫电池、电解液、隔膜方面的应用研究进展。

Modification of Nano-α-Al2O3 and Its Influence on the Surface Properties of Waterborne Polyurethane Resin Composite Passivation Films

Silane coupling agent KH560 was used to modify the surface of nano-α-Al2O3 in ethanol-aqueous solution with different proportions. The particle size of nano-α-Al2O3 was determined by nano-particle size analyzer, and the effects of nano-α-Al2O3 content, ethanol-aqueous solution ratio and KH560 dosage on the dispersion and particle size of nano-α-Al2O3 were investigated. The material structure before and after modification was determined by Fourier transform infrared spectroscopy (FTIR). Aqueous polyurethane resin and inorganic components are combined with modified nano-α-Al2O3 dispersion to form chromium-free passivation solution. The solution is coated on the galvanized sheet, the adhesion and surface hardness are tested, the bonding strength of the coating and the surface hardness of the substrate are discussed. The corrosion resistance and surface morphology of the matrix were investigated by electrochemical test, neutral salt spray test and scanning electron microscope test. The chromium-free passivation film formed after the modification of nano-α-Al2O3 increases the surface hardness of galvanized sheet by about 85%. The corrosion resistance of the film is better than that of a single polyurethane film. The results show that the surface hardness and corrosion resistance of polyurethane resin composite passivation film are significantly improved by the introduction of nano-α-Al2O3.

NH_(3)SO_(3)改性稀土尾矿催化剂NH_(3)-SCR脱硝活性及SO_(2)/H_(2)O耐受性能研究

采用球磨、微波焙烧方法制备了不同质量分数NH_(3)SO_(3)改性稀土尾矿NH_(3)-SCR脱硝催化剂。通过BET、SEM-EDS、XRD、NH_(3)-TPD、H_(2)-TPR分析了催化剂脱硝活性及SO_(2)/H_(2)O耐受性能。结果表明:NH_(3)SO_(3)改性使催化剂脱硝活性得到了显著提高,10%NH_(3)SO_(3)改性催化剂在300~350℃脱硝活性可达90%左右。SO_(2)/H_(2)O共同作用可将10%NH_(3)SO_(3)改性催化剂脱硝活性提高至97%,其促进作用保持了良好的稳定性,且具有可逆性。NH_(3)SO_(3)改性稀土尾矿后,催化剂比表面积、酸性位点及强度增加,表面活性物质分散度更高,弱化了尾矿矿物晶型,提高了催化剂吸附能力和氧化还原能力,从而提高催化脱硝活性,同时具备优良的SO_(2)/H_(2)O耐受性。

Dielectric barrier discharge plasma synthesis of Ag/γ-Al_(2)O_(3) catalysts for catalytic oxidation of CO

In this study,Ag/γ-Al_(2)O_(3)catalysts were synthesized by an Ar dielectric barrier discharge plasma using silver nitrate as the Ag source andγ-alumina(γ-Al_(2)O_(3))as the support.It is revealed that plasma can reduce silver ions to generate crystalline silver nanoparticles(Ag NPs)of good dispersion and uniformity on the alumina surface,leading to the formation of Ag/γ-Al_(2)O_(3)catalysts in a green manner without traditional chemical reductants.Ag/γ-Al_(2)O_(3)exhibited good catalytic activity and stability in CO oxidation reactions,and the activity increased with increase in the Ag content.For catalysts with more than 2 wt%Ag,100%CO conversion can be achieved at 300°C.The catalytic activity of the Ag/γ-Al_(2)O_(3)catalysts is also closely related to the size of theγ-alumina,where Ag/nano-γ-Al_(2)O_(3)catalysts demonstrate better performance than Ag/micro-γ-Al_(2)O_(3)catalysts with the same Ag content.In addition,the catalytic properties of plasma-generated Ag/nano-γ-Al_(2)O_(3)(Ag/γ-Al_(2)O_(3)-P)catalysts were compared with those of Ag/nano-γ-Al_(2)O_(3)catalysts prepared by the traditional calcination approach(Ag/γ-Al_(2)O_(3)-C),with the plasma-generated samples demonstrating better overall performance.This simple,rapid and green plasma process is considered to be applicable for the synthesis of diverse noble metal-based catalysts.

蛋壳型Ru/Al_(2)O_(3)催化剂的制备及其对邻苯二甲酸酯的加氢活性

采用等体积浸渍法,通过改变Ru前体溶液pH制备了一系列蛋壳型Ru/Al_(2)O_(3)催化剂,利用SEM、电子探针微区分析、XRD、H_(2)-TPR等方法考察了不同前体溶液对催化剂Ru活性组分分布的影响,并以邻苯二甲酸二(2-乙基己)酯(DEPH)为反应物,评价了催化剂的加氢性能。实验结果表明,随前体溶液pH升高,活性组分Ru浸渍厚度变薄,形成蛋壳型催化剂。活性组分Ru浸渍厚度较小时,反应受内扩散影响较小;Ru浸渍厚度较大时,反应受内扩散影响较大。Ru浸渍厚度为190μm时,所制备催化剂对DEPH的加氢活性最高。

Cu掺杂Ru/Al_(2)O_(3)催化剂催化环己醇空气氧化合成环己酮的研究

环己酮作为一种重要的有机化工原料,常用于制造己二酸和己内酰胺,并且广泛应用于纤维、合成橡胶、工业涂料、医药、农药和有机溶剂等工业领域。以H_(2)O_(2)做氧化剂,通过相转移催化剂催化或杂多酸为催化剂可实现环己醇氧化制备环己酮。然而,高浓度H_(2)O_(2)的强腐蚀性和易爆危险性,以及制备工艺的繁琐性使其应用受到限制。因此,寻求安全且成本低廉的催化工艺成为研究重点。本文以Cu掺杂Ru/Al_(2)O_(3)作为催化剂,空气为氧化剂,在釜式工艺下研究环己醇的氧化反应,考察了反应溶剂、温度、压力、催化剂组分等对反应的影响。

Al/Cr_(2)O_(3)对硝化棉热分解过程的影响

为了探讨Al/Cr_(2)O_(3)纳米铝热剂对硝化棉(NC)热分解过程的影响,采用差示扫描量热法(DSC)及热重/红外联用技术(TG/DTG-FTIR)研究了单组分NC和Al/Cr_(2)O_(3)/NC复合物的热分解反应过程。运用Kissinger法、Starink法、Kissinger-迭代法和Ozawa-迭代法计算得到NC及Al/Cr_(2)O_(3)/NC的表观活化能。通过FWO法、KAS法和Friedman法得到NC和Al/Cr_(2)O_(3)/NC热分解过程的动力学参数,并引入修正后的?esták-Berggren经验方程对相应热分解反应动力学模型进行重建。结果表明,Al/Cr_(2)O_(3)纳米铝热剂可使NC热分解反应的表观活化能降低33.7kJ/mol,热点火温度降低3.5℃,热爆炸临界温度降低3.0℃。Al/Cr_(2)O_(3)/NC的热分解反应过程遵循n级动力学方程f(α)=7.25α^(0.73)(1-α)^(2.12)。在Al/Cr_(2)O_(3)催化作用下,NC首先断裂O—NO_(2)键,最终释放H_(2)O、CO_(2)、CO、NO_(2)、NO、N_(2)O、HCHO和HCOOH气体产物。

Local structural evolutions of CuO/ZnO/Al2O3 catalyst for methanol synthesis under operando conditions studied by in situ quick X-ray absorption spectroscopy

In situ quick X-ray absorption spectroscopy(QXAFS) at the Cu and Zn K-edge under operando conditions has been used to unravel the Cu/Zn interaction and identify possible active site of CuO/ZnO/Al_2O_3 catalyst for methanol synthesis. In this work, the catalyst, whose activity increases with the reaction temperature and pressure, was studied at calcined, reduced, and reacted conditions. TEM and EDX images for the calcined and reduced catalysts showed that copper was distributed uniformly at both conditions. TPR profile revealed two reduction peaks at 165 and 195 °C for copper species in the calcined catalyst. QXAFS results demonstrated that the calcined form consisted mainly of a mixed Cu O and Zn O, and it was progressively transformed into Cu metal particles and dispersed Zn O species as the reduction treatment. It was demonstrated that activation of the catalyst precursor occurred via a Cu^+intermediate, and the active catalyst predominantly consisted of metallic Cu and Zn O evenunder higher pressures. Structure of the active catalyst did not change with the temperature or pressure, indicating that the role of the Zn was mainly to improve Cu dispersion.This indicates the potential of QXAFS method in studying the structure evolutions of catalysts in methanol synthesis.

The nature of the deactivation of hydrothermally stable Ni/SiO2–Al2O3 catalyst in long-time aqueous phase hydrogenation of crude 1,4-butanediol

The deactivation of Ni/SiO2-Al2 O3 catalyst in hydrogenation of crude 1,4-butanediol was investigated.During the operation time of 2140 h,the catalyst showed slow activity decay.Characterization results,for four spent catalysts used at different time,indicated that the main reason of the catalyst deactivation was the deposition of carbonaceous species that covered the active Ni and blocked mesopores of the catalyst.The TPO and SEM measurements revealed that the carbonaceous species included both oligomeric and polymeric species with high C/H ratio and showed sheet.Such carbonaceous species might be eliminated through either direct H2 reduction or the combined oxidation-reduction methodologies.

The effect of Al3+ coordination structure on the propane dehydrogenation activity of Pt/Ga/Al2O3 catalysts

The effect of the Al2O3 structure on the performance of Pt/Ga/Al2O3 catalysts is investigated for the direct dehydrogenation of propane. The study unveils that the structure of Al3+determines the bulk structure of catalysts, particularly a high content of coordinatively unsaturated Al3+sites(penta-coordinated Al3+,denoted as Al3+penta) could lead to a remarkably improved dehydrogenation activity of the catalyst. The bulk characterization reveals that the sufficient amount of Al3+pentain Al2O3 benefit the dispersion of Pt and Ga2O3 on the Al2O3 support. At the same time, TPR results reveal that the presence of Pt facilitates the reduction of Ga2O3, likely due to the hydrogen spillover between the well dispersed Pt and Ga2O3,which consequently enhances the synergistic function between Pt and Ga2O3 in the dehydrogenation of propane. Recyclability tests demonstrate that the dehydrogenation activity stabilizes after three cycles over the Pt/Ga/Al2O3 catalyst.

Oscillations during partial oxidation of methane to synthesis gas over Ru/Al_2O_3 catalyst

Oscillations in temperatures of catalyst bed as well as concentrations of gas phase species at the exit of reactor were observed during the partial oxidation of methane to synthesis gas over Ru/Al2O3 in the temperature range of 600 to 850℃. XRD, H2-TPR and in situ Raman techniques was used to characterize the catalyst. Two types of ruthenium species, i.e. the ruthenium species weakly interacted with Al2O3 and that strongly interacted with the support, were identified by H2-TPR experiment. These species are responsible for two types of oscillation profiles observed during the reaction. The oscillations were the result of these ruthenium species switching cyclically between the oxidized state and the reduced state under the reaction condition. These cyclic transformations, in turn, were the result of temperature variations caused by the varying levels of the strongly exothermic CH4 combustion and the highly endothermic CH4 reforming （with H2O and CO2） reactions （or the less exothermic direct partial oxidation of methane to CO and H2）, which were favored by the oxidized and the metallic sites, respectively. The major pathway of synthesis gas formation over the catalyst was via the combustion-reforming mechanism.

CO_2 methanation over TiO_2–Al_2O_3 binary oxides supported Ru catalysts

TiO_2 modified Al_2O_3 binary oxide was prepared by a wet-impregnation method and used as the support for ruthenium catalyst. The catalytic performance of Ru/TiO_2–Al_2O_3catalyst in CO_2 methanation reaction was investigated. Compared with Ru/Al_2O_3 catalyst, the Ru/TiO_2–Al_2O_3catalytic system exhibited a much higher activity in CO_2 methanation reaction. The reaction rate over Ru/TiO_2–Al_2O_3 was 0.59 mol CO_2·(g Ru)1·h-1, 3.1 times higher than that on Ru/Al_2O_3[0.19 mol CO_2·(gRu)-1·h-1]. The effect of TiO_2 content and TiO_2–Al_2O_3calcination temperature on catalytic performance was addressed. The corresponding structures of each catalyst were characterized by means of H_2-TPR, XRD, and TEM. Results indicated that the averaged particle size of the Ru on TiO_2–Al_2O_3support is 2.8 nm, smaller than that on Al_2O_3 support of 4.3 nm. Therefore, we conclude that the improved activity over Ru/TiO_2–Al_2O_3catalyst is originated from the smaller particle size of ruthenium resulting from a strong interaction between Ru and the rutile-TiO_2 support, which hindered the aggregation of Ru nanoparticles.

催化剂中Rh含量对NH_(3)及N_(2)O生成量影响研究

研究了不同Rh含量的三效催化剂对CO和NO_(x)的起燃性能,并对反应过程中副产物NH_(3)以及N_(2)O的生成规律进行研究。实验通过浸渍法制备得到不同Rh含量的Rh-Pd/Ce_(x)Zr_(1-x)O_(2)+La-Al_(2)O_(3)催化剂,采用一套专用多路固定床连续流动模拟气反应器对其性能进行评价。研究结果表明:不同Rh负载量表现出不同的N_(2)选择性,随着Rh用量的增加NO_(x)的转化性能提升。总体来看,低Rh用量的催化剂产生更多的N_(2)O和NH_(3)副产物,而随着Rh用量的增加其N_(2)选择性也增加。当温度达到400℃时,Rh用量≥0.141 g/L的催化剂基本没有N_(2)O生成,Rh用量≥0.283 g/L基本没有N_(2)O和NH_(3)生成。该研究对于优化三效催化剂中Rh配比以提升N_(2)选择性具有借鉴意义,并对于设计满足未来国Ⅶ排放标准的三效催化剂具有重要的指导意义。

金属离子修饰的Ru-Pt/γ-Al_2O_3催化p-CNB选择性加氢

The bimetallic catalyst Ru-Pt/ γ -Al 2O 3 was prepared by impregnating H 2PtCl 6 and RuCl 3 aqueous solution in the presence of PVP(40 000). Its catalytic performance in selective hydrogenation of \{ p -chloronitrobenzene\}( p -CNB) was studied. The results indicate that the activity of Ru-Pt/ γ -Al 2O 3[\{ n (ruthenium)\}∶ n (platinum)=4∶1] is much higher than that of Ru/ γ -Al 2O 3,while the amount of dehalogenation product(aniline) and other by-products are much fewer than that by using Pt/ γ -Al 2O 3 as the catalyst. There is synergistic effect of ruthenium and platinum in bimetallic catalyst for selective hydrogenation of p -CNB. Under the reaction conditions t =50 ℃, p H 2 = 1.0 MPa, reaction time 60 min,\{ n (substrate)∶\} n (total amount of metal content)=1000∶1,the conversion of p -CNB and the selectivity to p -chloroaniline( p -CNA) by using Ru-Pt/ γ -Al 2O 3 as the catalyst are 48.2% and 85.9%,respectively. The effect of other metal cations(introduced to the reaction system with the corresponding metal chloride solution) on the reaction was investigated. It was found that catalytic performance of Ru-Pt/ γ -Al 2O 3 could be greatly improved by modfication of some metal cations. When Co 2+ and Ni 2+ were used as modifiers for the catalyst Ru-Pt/ γ -Al 2O 3 under above mentioned reaction conditions,the conversions of p -CNB increase to 74.5% and 87.8%,as well as the selectivities of p -CAN increase to 98.9% and 99.4%,respectively. Fe 3+ and Sn 4+ were the best modifiers for Ru-Pt/ γ -Al 2O 3 under the same reaction conditions. The conversions of p -CNB and the selectivities of p -CAN can reach 100% and >99.0%,respectively. However,the catalysts can be poisoned by Zn 2+ and Sn 2+ .

纳米Al_2O_3负载Ru催化剂用于CO_2加氢合成甲酸研究

为了研究载体性质对Ru负载型催化剂的CO2加氢合成甲酸反应性能的影响,制备了以Al2O3纳米棒和γ-Al2O3为载体的一系列Ru基催化剂,采用透射电镜(TEM)、X射线衍射(XRD)、D2/OH交换和程序升温还原(H2-TPR)等方法详细表征催化剂的性质,并考察CO2加氢制甲酸的反应性能。结果表明:与传统Ru/Al2O3催化剂相比,以Al2O3纳米棒为载体时,Ru Ox物种在载体表面的分散程度高,Al2O3纳米棒的表面OH数目多,有利于提高催化剂的反应活性,另外当Ru在Al2O3纳米棒上的负载量(质量分数)为1%时,甲酸产量最高可以达到11.7mmol/h。

铈掺杂Ru/Al_2O_3催化臭氧氧化降解邻苯二甲酸二甲酯

考察了铈(Ce)的掺杂对Ru/Al2O3催化臭氧氧化邻苯二甲酸二甲酯(DMP)溶液过程的影响.结果表明,Ce的掺杂可以显著提高臭氧氧化的效果,反应100min后,TOC的去除率可以由原催化剂的61.3%提高到75.1%,而单独臭氧氧化仅有14.0%.在实验范围内,Ru和Ce同时浸渍催化效果较好,且活性组分的溶出最少,Ce的最佳掺杂量为1.0%.通过催化剂吸附试验、单独臭氧氧化试验、Ce的均相催化试验及Ru-Se/Al2O3催化剂的非均相催化实验,证明Ru-Ce/Al2O3催化剂对DMP溶液臭氧氧化体系TOC的去除率达到50%,这是基于Ru-Ce/Al2O3催化剂的非均相催化作用.

Cu-Fe-Ru-La/γ-Al_2O_3湿式氧化催化剂的制备、表征及机理(英文)

采用等量浸渍法以γ-Al2O3为载体,制备过渡金属Cu和Fe、贵金属Ru、稀土金属La的复合催化剂。采用催化湿式空气氧化法处理模拟印染废水,研究金属离子配比、焙烧温度对催化剂活性及稳定性的影响,并对催化剂CWAO反应机理进行探讨:权衡催化剂的活性和稳定性,催化剂的组分质量配比和焙烧温度分别为Cu∶Fe∶Ru∶La=1∶1∶1∶3、450℃。对催化剂进行XRD、XPS、孔结构、FT-IR、TG-DTA、SEM、TEM表征,结果表明:焙烧使催化剂组成物质分解为氧化物,元素Cu、Fe、Ru、La分别以CuO、Fe2O3、RuO2、La2O3形式存在;焙烧温度升高,晶粒长大结晶趋于完整,催化剂孔容孔径增大但比表面积减小,晶粒尺寸分布在5～20 nm;Cu-Fe-Ru-La/γ-Al2O3催化剂使用前后结构无明显变化且反应后溶出的金属浓度低,催化剂具有较高的稳定性。

湿式氧化催化剂RuO_2/γ-Al_2O_3的制备及降解苯酚的研究

采用浸渍法制备了 4 %质量分数的RuO2 /γ Al2 O3 催化剂 ,并利用XRD和SEM对催化剂进行了晶体结构表征。研究了催化剂制备的焙烧温度和时间、进水pH值和处理温度对RuO2 /γ Al2 O3 催化剂活性影响 ,并对其影响机制进行了初步探讨。结果表明 ,焙烧温度升高、焙烧时间延长会导致催化剂的活性组分RuO2 的晶粒增长过大 ;在 30 0℃经 3h焙烧 ,形成的RuO2 晶粒细小 ,苯酚溶液的COD(化学需氧量 )去除率较高。在本研究的pH范围内 ,进水pH值为酸性时 ,COD去除率高于碱性时的COD去除率 ;当反应温度升高时 ,RuO2 /γ Al2 O3 催化剂降解苯酚的能力显著提高 ,且反应的诱导期明显缩短 ,当反应温度从 15 0℃升高至 180℃时 ,在进水pH值为 5 .6 ,反应 2h后 ,此催化剂的COD去除率为 96 %以上。研究表明 ,RuO2 /γ Al2 O3 催化剂具有较好的活性和和稳定性。