CN106232227A - 合成用于环氧化反应的负载金(au)纳米颗粒的方法 - Google Patents
合成用于环氧化反应的负载金(au)纳米颗粒的方法 Download PDFInfo
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- CN106232227A CN106232227A CN201580021173.4A CN201580021173A CN106232227A CN 106232227 A CN106232227 A CN 106232227A CN 201580021173 A CN201580021173 A CN 201580021173A CN 106232227 A CN106232227 A CN 106232227A
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- gold
- solution
- phosphorus compound
- complex
- metal hydroxides
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- -1 phosphorus compound Chemical class 0.000 claims abstract description 57
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- 125000002769 thiazolinyl group Chemical group 0.000 description 1
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Classifications
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- C07D301/02—Synthesis of the oxirane ring
- C07D301/03—Synthesis of the oxirane ring by oxidation of unsaturated compounds, or of mixtures of unsaturated and saturated compounds
- C07D301/04—Synthesis of the oxirane ring by oxidation of unsaturated compounds, or of mixtures of unsaturated and saturated compounds with air or molecular oxygen
- C07D301/08—Synthesis of the oxirane ring by oxidation of unsaturated compounds, or of mixtures of unsaturated and saturated compounds with air or molecular oxygen in the gaseous phase
- C07D301/10—Synthesis of the oxirane ring by oxidation of unsaturated compounds, or of mixtures of unsaturated and saturated compounds with air or molecular oxygen in the gaseous phase with catalysts containing silver or gold
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Abstract
提供了用于制备负载金纳米颗粒催化剂的方法。在示例性实施方式中,所述方法包括将磷化合物的溶液添加至氯(二甲基硫醚)金(I)的溶液以获得氯(磷化合物)金(I)复合物的溶液,将所述氯(磷化合物)金(I)复合物的溶液添加至硝酸银的溶液以获得硝基(磷化合物)金(I)复合物的溶液,将所述硝基(磷化合物)金(I)复合物的溶液施加至金属氢氧化物载体,干燥所述金属氢氧化物载体;以及锻烧干燥的金属氢氧化物载体以形成负载金纳米颗粒催化剂。还提供了由所述方法制备的负载金纳米颗粒催化剂,以及在所述负载金纳米颗粒催化剂的存在下将乙烯氧化为环氧乙烷的方法。
Description
技术领域
本公开的主题涉及用于制备负载金纳米颗粒催化剂(supported goldnanoparticle catalyst)的方法、由此制备的负载金纳米颗粒催化剂、以及在该负载金纳米颗粒催化剂的存在下将乙烯氧化为环氧乙烷(ethylene oxide)的方法。
背景技术
在用于制造用于大范围的下游市场的许多产品的许多工业过程中,环氧乙烷是一种重要的化学中间体。环氧乙烷在室温下是无色的气体并且在10℃下凝结成液体。环氧乙烷能与水和许多其他的有机溶剂如醇和醚混溶。在表1中总结了环氧乙烷的另外的物理和化学性质。环氧乙烷的反应性归因于其高度染色(highly stained)的三元环。
表1-环氧乙烷的物理性质
性质 | 值 |
在101.3kPa下的沸点(℃) | 10.4 |
熔点(℃) | -112.4 |
在25℃下的燃烧热(kJ/mol) | 1306.04 |
在1atm下的汽化热(cal.g) | 136.1 |
密度 | 0.8711 |
在空气中的分解温度(℃) | 560 |
偶极矩(c-m) | 634×10-30 |
可溶性 | 水、丙酮、苯 |
可以通过非催化的水解反应将环氧乙烷转化为乙二醇。采用乙二醇作为用于生产如聚对苯二甲酸乙二醇酯的聚合物的原材料,并且可以用作机动车的抗冷冻添加剂。环氧乙烷还用于生产乙醇胺、溶剂、表面活性剂等。图1示出了由环氧乙烷获得的各种产物。
也可以通过氯代醇方法生产环氧乙烷。在这种方法中,反应通过在图2中示出的两个连续反应进行。首先,作为氯与水反应的结果形成次氯酸,并与乙烯反应以形成氯乙醇和盐酸。其次,如在图2中示出的,在碱如氢氧化钙的存在下,发生氯从氯乙醇中分子间置换(Monison,et al.,Organic Chemistry,Fifth Edition,Allyn and Bacon,Inc.:Boston,1987,p.713)。
在负载银类催化剂(supported silver based catalyst)上乙烯至环氧乙烷的直接多相催化氧化已经替代了氯代醇方法。这种方法的一个方面是选择使乙烯完全氧化成CO2最小化的催化剂系统。至二氧化碳和水的主要途径是通过乙烯的直接氧化或者环氧乙烷的进一步氧化(Schonfeldt,et al.,Surface Active Ethylene Oxide Adducts,SecondEdition,Pergamon Press Ltd.:Hungary,1969,p.25;Kilty,et al.,The Mechanism ofthe Selective Oxidation of Ethylene to Ethylene Oxide.Catalyst Reviews(1974):10(1):1)。
此外,用于将环氧乙烷转化为二氧化碳和水的路径是通过其异构化产物乙醛(Weissermel et al.)。在商业过程中,作为乙烯的直接氧化的结果,检测到较少量的甲醛(Raben,F.Ethylene Oxide Manufacturing Process.Reviews in Process Chemistryand Engineering(1999):2(1):53)。选择性和转化率可以直接受催化剂的性质和反应条件的影响。图3显示了来自乙烯的直接氧化的主要产物。图3中的所有的ΔH值是使用298K下的ΔHf值计算的(Atkins,P.W.Physical Chemistry,Fifth Edition,Oxford UniversityPress,London(1994):C9-C10)。
银-氧相互相用是涉及乙烯环氧化的重要过程。许多研究已经着手进行以阐明银金属和氧之间的化学相互相用,如吸附、解吸、表面污染的效应和一些晶体银相的反应性(Czanderna A.W.The Adsorption or Oxygen on Silver,The Journal of PhysicalChemistry(1964);68(10),2765)。
已经公开了在气相中乙烯选择性氧化为环氧乙烷的机理。可以将分子氧解离地化学吸附以形成原子氧或者非解离地化学吸附以产生表面结合的氧分子。随后分子氧与乙烯反应以产生环氧乙烷,同时原子氧反应以产生完全氧化的产物。以上指出的Cazandera的文章提出了在如下三个过程中使氧吸附在银金属上的机理。首先,低活化能(3kcal mol-1),在四个邻近的银原子上的氧分子解离吸附。
O2+4Ag(邻近)→2O2-(吸附)+4Ag+(邻近)
第二过程发生在其中不可获得四个邻近的银原子的位置。这导致具有高于第一过程的活化能的分子氧吸附(8kcal mol-1)。
O2+Ag→O2 -(吸附)+Ag+
第三过程是在四个非邻近的银原子上的氧解离吸附以形成吸附的原子氧和四个邻近的银原子。这是在升高的温度下通过表面氧迁移发生的并且具有更高的活化能(14kcal mol-1)。
O2+4Ag(非邻近)→2O2-(吸附)+4Ag+(邻近)
长时间以来,金属金作为催化剂被认为是非活性的。在催化中宏观的较大金颗粒的不良活性和惰性归因于其较低的化学吸附亲合性以及在金表面上氧的化学吸附的负焓(Hammer,et al.,Gold Is the Noblest of All the Metals,Nature(1995);376:238)。后者是进入的分子或原子的分子轨道或原子轨道与金的d轨道之间的较弱的重叠。然而,已知在特定条件下金可以展现出较高的催化活性(Bond,G.Gold:a Relatively New Catalyst,Catalysis Today(2002);72:5)。当将金负载在作为细纳米颗粒的金属氧化物的表面上时,其可以显示出显著的反应性并且在许多催化反应中是有利的,如水煤气变换(water gasshift)(Tabakova et al.,Influence of the Microscopic Properties of the Supporton the Catalytic Activity on Au/ZnO,Au/Fe2O3,Au/Fe2O3-ZnO,Au/Fe2O3-ZrOCatalysts for the WGS Reaction,Applied Catalysis A,2000,202,91),乙炔的氯氢化(Thomson,New Advances in Gold Catalysis,Part 1.Gold Bulletin(1998);31(4):111),一氧化碳的氧化(Grunwaldt et al.,Preparation of Supported Gold Catalystfor Low-Temperature CO Oxidation Via Size-Controlled Gold Colloids,Journal ofCatalysis(1999);181:223;Haruta et al.,Advances in the Catalysis of AuNanoparticles,Applied Catalysis(2001);222:427),氮氧化物至氮气的还原(Ueda etal.,Nitric Oxide Reduction with Hydrogen,Carbon Monoxide,and HydrocarbonsOver Gold Catalysis,Gold Bulletin(1999);32:1),氢化作用(Mohr et al.,TheInfluence of Real Structure of Gold Catalyst in the Partial Hydrogenation ofAcrolein,Journal of Catalysis(2003);213:86),以及选择性氧化(Morrison et al.,Thomas,New Advances in Gold Catalysis,Part II,Gold Bulletin(1999);32(1);Mulet al.,Stability and Selectivity of Au/TiO2and Au/TiO2/SiO2 Catalysts inPropane Epoxidation:An in Situ FT-IR Study,Journal of Catalysis(2001);201:128;Uphade et al.,Vapor-Phase Epoxidation of Propane Using H2 and O2 Over Au/Ti-MCM-48,Journal of Catalysis(2002);209:331;WO 2003/062196)。此外,已经在丙烯的直接环氧化中使用了活化的负载金纳米颗粒(Grunwaldt et al.;Mul et al.;Uphadeet al.;WO 2003/062196)。
Richardson等人研究了在宽范围的温度(25-405℃)下在金薄膜上分子氧的吸附(Richardson et al.,The Absorption of Oxygen on Evaporated Gold Films,Journalof Catalysis(1970);46:420)。发现在25-230℃的温度范围内不发生氧的吸附,而在341℃下出现低覆盖度(coverage)(θ=0.3)并且在405℃下实现最大覆盖度(θ=0.7)。Pireaux使用高分辨率电子能量损失谱(HREED)、X射线光电子能谱(XPS)和俄歇能谱(Augerspectroscopy),表征了在洁净的金表面上的氧吸附(Pireaux et al.,SpectroscopyCharacterization of Oxygen Absorption on Gold Surfaces.II.Production of GoldOxide in Oxygen DC Reactive Sputtering,Surface Science(1984);141:221)。发现在100-800K的温度范围内分子氧不吸附在Au(110)和Au(111)晶面上。然而,还提出氧分子可以吸附在带负电的金团簇(cluster)上(Salisbury et al.,Low-Temperature Activationof Molecular Oxygen by Gold Clusters:As Stoichiometric Process Correlation toElectron Affinity.Chemical Physics(2000);262:131)。Mills报道了在中性的和带电荷的金团簇上分子氧的吸附(Mills et al.,The Absorption of Molecular Oxygen onNeutral and Negative Aun clusters(n=2-5),Chemical Physics Letters(2002);306:493)。此外,Franceschetti等人报道了在金团簇上氧分子的吸附,具有0.5至1.5ev结合能(Franceschetti et al.,Oxygen chemisorptions on Au Nanoparticles,ChemicalPhysics(2003);274:471)。Francescheui等人发现,分子吸附的氧的结合能小于包含接近线性的O-Au-O桥的解离吸附的原子氧的结合能。Salisbury提出氧分子作为一个电子受体起作用并且作为稳定的超氧化物离子O2 -结合至金纳米颗粒(Salisbury et al.)。超氧化物离子的稳定性归因于在π*反键轨道中的未配对电子的数量从两个电子减少至一个(Salisbury et al.)。
在本领域中仍存在对减少乙烯至二氧化碳的氧化作用的用于选择性氧化乙烯为环氧乙烷的改善的催化剂的需要。
发明内容
本文中公开了用于制备负载金纳米颗粒催化剂(supported gold nanoparticlecatalyst)的方法。本方法包括将磷化合物的溶液添加至氯(二甲基硫醚)金(I)(chloro(dimethyl sulfide)gold(I))的溶液以获得氯(磷化合物)金(I)复合物(chloro(phosphorus compound)gold(I)complex)的溶液,其中磷化合物可以是具有式PR1R2R3的膦、具有式P(OR4)R5R6的次膦酸酯(phosphinite)、具有式P(OR7)(OR8)R9的亚膦酸酯(phosphonite)、具有式P(OR10)(OR11)(OR12)的亚磷酸酯(phosphite)或它们的组合。R1至R12可以各自是烷基、可选地取代的烷基、芳基、可选地取代的芳基、芳烷基、可选地取代的芳烷基或它们的组合。该方法进一步包括将氯(磷化合物)金(I)复合物的溶液添加至硝酸银的溶液以获得硝基(磷化合物)金(I)复合物(nitro(phosphorus compound)gold(I)complex)的溶液,将硝基(磷化合物)金(I)复合物的溶液施加至金属氢氧化物载体,干燥该金属氢氧化物载体;以及锻烧该干燥的金属氢氧化物载体以形成负载金纳米颗粒催化剂。在一些实施方式中,烷基可以是异丙基、环己基、叔丁基、乙基或它们的组合。在一些实施方式中,芳基是苯基。在一些实施方式中,可选地取代的芳基是均三甲苯基(mesityl)、2,6-二甲氧基苯基、4-甲氧基苯基、l-萘基、4-甲基苯基或它们的组合。在一些实施方式中,芳烷基是苄基。在某些非限制性的实施方式中,磷化合物是具有式PR1R2R3的膦。
在非限制性的实施方式中,金属氢氧化物是氢氧化铝、氢氧化镁、氢氧化锌、氢氧化铁、氢氧化镍、氢氧化钛或它们的组合。在一些实施方式中,金属氢氧化物是通过水解氢氧化钾溶液中的金属获得的。在一个实施方式中,金属氢氧化物是氢氧化钛,并且氢氧化钛是通过水解氢氧化钾溶液中的四异丙醇钛(titanium-tetra-isopropoxide)获得的。在某些实施方式中,水解在约5至约10的pH值下进行。可以通过添加氢氧化钾溶液调节pH值。
在某些实施方式中,在连续搅拌约12小时下,将硝基(磷化合物)金(I)复合物的溶液施加至金属氢氧化物。在真空下在约20℃至约25℃的温度下将金属氢氧化物干燥。在约100℃至约300℃的温度下煅烧干燥的金属氢氧化物。在一些实施方式中,在惰性的氮气气氛中进行该过程。此外,该过程可以进一步包括,在施加硝基(磷化合物)金(I)复合物的溶液至金属氢氧化物载体之前,添加碱性促进剂(alkali promoter)至硝基(磷化合物)金(I)复合物的溶液。在一个实施方式中,碱性促进剂是铯。
本公开主题还提供了通过以上描述的方法制备的负载金纳米颗粒催化剂。在一些实施方式中,金纳米颗粒的尺寸是约2nm至约15nm。在本公开主题的非限制性实施方式中,负载金纳米颗粒催化剂包含按重量计约0.1%至约5%的硝基(三烷基膦)金(I)复合物。
此外,本公开的主题提供了用于将乙烯氧化为环氧乙烷的方法。该方法包括在以上描述的负载金纳米颗粒催化剂的存在下使乙烯和氧反应。在一些实施方式中,该方法在固定床流动反应器(fixed bed flow reactor)中进行。在某些实施方式中,将惰性气体进料至氧化过程。在一种实施方式中,惰性气体是氩气。
附图说明
图1显示了由环氧乙烷获得的产物。
图2示出了通过氯代醇方法(chlorohydrin process)的环氧乙烷的合成。
图3示出了乙烯的直接氧化。
图4示出了根据本公开主题的一个非限制的示例性实施方式用于合成负载金纳米颗粒催化剂的方法。
图5显示了在由根据本公开主题的一个非限制的示例性实施方式的方法制备的负载金纳米颗粒催化剂的存在下,用于将乙烯氧化为环氧乙烷的反应器系统。
图6显示了在由根据本公开主题的一个非限制的示例性实施方式的方法制备的负载金纳米颗粒催化剂上,用于将乙烯选择性氧化为环氧乙烷的一种机理。
图7显示了在由根据本公开主题的一个非限制的示例性实施方式的方法制备的负载金纳米颗粒催化剂上,用于将乙烯选择性氧化为环氧乙烷的一种机理。
具体实施方式
本公开主题提供了用于制备负载金纳米颗粒催化剂的方法、由此制备的负载金纳米颗粒催化剂、以及在该负载金纳米颗粒催化剂的存在下将乙烯氧化为环氧乙烷的方法。
负载金纳米颗粒催化剂的合成
根据本公开的主题,该合成方法在惰性的氮气气氛中进行。该方法可以在具有弱光条件的手套箱内进行。根据本公开的主题合成负载纳米颗粒金催化剂的示例性方法可以包括:(i)合成磷化合物配体;(ii)合成氯(磷化合物)金(I)复合物(例如氯(烷基膦)金(I)复合物(chloro(alkyl-phosphine)gold(I)complex)(R1R2R3PAuCl));(iii)合成硝基(磷化合物)金(I)复合物(例如硝基(烷基膦)金(I)复合物(nitro(alkyl phosphine)gold(I)complex)),以及(iv)合成负载金纳米颗粒(supported gold nanoparticle)。现在按顺序描述每一个。
1.磷化合物配体的合成
可以由各种商业来源获得磷化合物配体。例如,可以从Aldrich Company获得除了三萘基膦之外的所有的叔膦。三萘基膦可以购自Alfa Company。
2.氯(磷化合物)金(I)复合物的合成
可以通过添加磷化合物的溶液至氯(二甲基硫醚)金(I)的溶液来合成氯(磷化合物)金(I)复合物。在某些实施方式中,磷化合物是具有式PR1R2R3的膦。R1、R2和R3各自可以是烷基、可选地取代的烷基、芳基、可选地取代的芳基、芳烷基、或可选地取代的芳烷基。R1、R2和R3可以是彼此相同或不同的。
在某些实施方式中,磷化合物是具有式P(OR4)R5R6的次膦酸酯。R4、R5和R6各自可以是烷基、可选地取代的烷基、芳基、可选地取代的芳基、芳烷基、或可选地取代的芳烷基。R4、R5和R6可以是彼此相同或不同的。
在某些实施方式中,磷化合物是具有式P(OR7)(OR8)R9的亚膦酸酯。R7、R8和R9各自可以是烷基、可选地取代的烷基、芳基、可选地取代的芳基、芳烷基、或可选地取代的芳烷基。R7、R8和R9可以是彼此相同或不同的。
在某些实施方式中,磷化合物是具有式P(OR10)(OR11)(OR12)的亚磷酸酯。R10、R11和R12各自可以是烷基、可选地取代的烷基、芳基、可选地取代的芳基、芳烷基、或可选地取代的芳烷基。R10、R11和R12可以是彼此相同或不同的。
在某些实施方式中,烷基是异丙基、环己基、叔丁基、或乙基。在某些实施方式中,芳基是苯基。在某些实施方式中,可选地取代的芳基是均三甲苯基、2,6-二甲氧基苯基、4-甲氧基苯基、l-萘基或4-甲基苯基。在某些实施方式中,芳烷基是苄基。
在一个非限制性的实例中,如在图4中示出的,可以将处于二氯甲烷中的三烷基膦的溶液逐滴地添加至处于二氯甲烷中的氯(二甲基硫醚)金(I)的溶液,具有膦配体与金复合物的相等摩尔比。通过缓慢添加正己烷至反应混合物,沉淀氯(三烷基膦)金(I)(R3PAuCl)复合物。然后,可以将产物滤去以去除所有剩余的二甲基硫醚和二氯甲烷。随后,将产物从正己烷和二氯甲烷的混合物中重结晶(Bruce et al.,Synthesis of Gold-Containing Mixed-Metal Cluster Complexes,Inorganic Synthesis(1989);26:324)。
3.硝基(磷化合物)金(I)复合物的合成
在一个非限制性的实施例中,如在图4中示出的,可以将处于二氯甲烷中的氯(三烷基膦)金(I)复合物的溶液添加至处于甲醇中的硝酸银的溶液。立即形成氯化银的白色沉淀。然后,可以搅拌混合物,例如,在室温下约一个小时,并且过滤溶液以去除氯化银粉末(Mueting et al.,Mixed-Metal-Gold Phosphine Cluster Compounds,InorganicSynthesis(1992);29:279)。通过缓慢去除溶剂,可以留下滤出液用于结晶。将产物从二氯甲烷和正己烷的混合物中重结晶。
4.负载金纳米颗粒的合成
金属氢氧化物载体可以是氢氧化铝、氢氧化镁、氢氧化锌、氢氧化铁、氢氧化镍、氢氧化钛或它们的组合。如在本领域中的普通技术人员所理解的,术语“金属氢氧化物”可以包括金属的各种氧化物和水合物。金属氢氧化物载体可以通过水解氢氧化钾水溶液中的金属(例如,铝、镁、锌、铁和镍)硝酸盐来获得。在一个实施方式中,金属氢氧化物是氢氧化钛。氢氧化钛通过水解氢氧化钾溶液中的四异丙醇钛获得。可以通过逐渐地添加氢氧化钾溶液调节pH值。可以将金属氢氧化物沉淀滤去并用蒸馏水反复洗涤。
在一个非限制性实例中,如在图4中示出的,在连续搅拌约12小时下,可以将如以上3描述获得的硝酸金复合物的丙酮溶液浸透入湿的金属氢氧化物中,例如以与由Kozlov描述的用于类似化合物的相似的方式(Kozlov et al.,Supported Gold CatalystsPrepared from a Gold Phosphine Precursor and As-Precipitated Metal-HydroxidePrecursor:Effect of Preparation Conditions on the Catalytic Performance,Journal of Catalysis(2000);196:56)。可以通过改变引入的金复合物的量来改变浸透溶液中的理论金属金浓度。可以在真空下在室温(20℃至约25℃)下干燥最终溶液,随后以2K/min的斜坡速率(ramping rate)锻烧处理至100℃至约300℃范围内的不同温度。
膦原子可以使得金的阳离子性更大,使得其与载体羟基基团更加强烈地相互作用,导致在热处理时形成非常小的颗粒。阳离子性较大的负载金纳米颗粒可以展现出用于乙烯选择性氧化为环氧乙烷的优异的催化性能。
本公开的主题还提供了通过以上描述的方法制备的负载金纳米颗粒。在负载金纳米颗粒催化剂中可以调节三个因素,以便获得优异的催化性能。第一个是载体的性质以及金纳米颗粒与载体表面的强相互作用以形成沉积的半球形纳米颗粒。载体对于提供其中可以吸附氧的表面阴离子空位(surface anion vacancy)是重要的。此外,载体中的多孔结构提供了较高的表面积。在某些实施方式中,本公开主题的负载金纳米颗粒催化剂包含氢氧化铝、Al2O3作为中性载体,氢氧化铁、Fe2O3作为可还原的金属氧化物载体,氢氧化镍、NiO作为可氧化的载体,氢氧化镁、氢氧化锌、MgO和ZnO作为碱性载体,氢氧化钛和TiO2作为酸性载体。
第二个因素是金的粒径,因为保持具有约0.5nm至约15nm(例如,约0.5nm至约5nm、或约2nm至约15nm)的粒径的超细金纳米颗粒对于催化性能是重要的。在一个实施方式中,金的粒径是约2nm至约15nm。当金的粒径减小时,由于键结构较弱,每个原子更多地表现为独立的原子,其可以使得金金属惰性较低。然而,由于可用于化学相互作用的表面分数(surface fraction)较低,非常小的负载金纳米颗粒(=0.8nm)示出用于CO氧化反应的非常小的催化活性(Salisbury et al.;Sanchez et al.,When Gold is Not Noble:Nanoscale Gold Catalysts,Journal of Physical Chemistry A(1999);103:9573)。
第三个因素是金纳米颗粒在载体的表面上的高分散性,其对于负载金催化剂的高催化活性可以是重要的(Haruta,Catalysis of Gold Nanoparticles Deposited onMetal Oxides.Cattech(2002);6(2):102)。所有的三个因素可以均受到制备负载金纳米颗粒的方法的影响。
可以通过将叔烷基膦金(I)硝酸盐复合物负载在金属氢氧化物载体上来合成本公开主题的负载金纳米颗粒催化剂。通过改变连接至膦原子的烷基基团,改变复合物的电和空间性质,以便影响粒径、载体上纳米颗粒的分散、以及与载体的相互相用。增加烷基基团的电负性(electron-negativity)导致稳定并降低膦的σ*轨道的能量。因此,膦上的空σ*轨道对于来自金属轨道的电子的反馈(back donation)是更加可进入的,这使得金的阳离子性更大,使得金与载体羟基基团的互相作用更强,导致在热处理时形成非常小颗粒。
烷基基团的空间尺寸也可以对金纳米颗粒在载体上的分散起作用。当一个金前体沉积在载体的表面上时,配体的尺寸可以限制接近载体的邻近羟基基团,因而控制金颗粒的沉积尺寸和纳米尺寸分布。此外,配体的改变影响处于固态的闭壳层(closed-shell)Au-Au亲金吸引(aurophilic attraction),并且可以对粒径和分散性具有直接的影响。电负性的或大体积的基团可以减小Au-Au相互作用能量,导致形成单体或二聚体分子(Toronto etal.,Solid State Structures and Gold-Gold Bonding in Luminescent Halo(dimethylphenylphosphine)gold(I)Complexes,Inorganic chemistry(1996);35:2484)。在另一方面,较低的电负性或较小的配体可以导致亲金相互相用能的增加并且形成分子的聚合物链(Mathiesona et al.,Preparation and Structural Characterization ofIsocyanide Gold(I)Nitrates,[Au(NO3)(CNR)](R=Et,BU1 or C6H3Me2-2,6);NewAurophilic Motifs,Journal of Chemical Society,Dalton Transaction(1999);2:201)。
金前体和负载金催化剂的表征
收集合成的三烷基膦金氯化物和硝酸盐复合物的红外(IR)光谱。新的强带出现在1499cm-1和1275cm-1,其是当氯化物转化为硝酸盐时,NO3-配体的特征。此外,使用IR分析,可以观察连接至磷的配体的C-H伸缩频率。由于与羟基基团的相互相用,IR也可以用于监测金前体在载体上的解离吸收。这可以通过观察NO3-带的消失以及对应于载体上的离子NO3-物质的1363cm-1附近新带的形成来实现(Yuan et al.,Supported Au Catalysts Preparedfrom Au Phosphine Complexes and As-Precipitated Metal Hydroxides:characterization and Low-Temperature CO Oxidation,Journal of Catalysis(1997);1780:191;Yuan et al.,Supported Gold Catalysis Derived from the Interaction ofa Au-Phosphine Complex with As-Precipitated Titanium Hydroxide and TitaniumOxide,Catalysis Today(1998);44:333)。可以采用元素分析以确定金复合物的化学组成。可以通过X射线荧光光谱分析金属金和磷。可以通过CHN微量分析来分析碳和氮。热重分析(TGA)可以用于确定复合物和催化剂前体的分解温度以及确定用于催化剂合成的合适温度。
暴露的金属金的表面积与实际的催化面积成比例(Satterfleld,HeterogeneousCatalysis in Industrial Practice,Second Edition,McGraw-Hill:New York,1996:139)。可以采用温度程序脱附(temperature programmed desorption)(TPD)技术通过测量一氧化碳气体的吸收来定量测量金纳米颗粒的表面积。还可以采用TPD技术用于研究表面氧覆盖对选择性和活性的影响。这可以通过测量在不同的覆盖百分比下表面上氧的结合强度来进行(Czanderna,Isosteric Heat of Absorption of Oxygen on Silver,Journalof Vacuum Science Technology(1977);14:408)。TPD实验可以在约6mm内径的U型石英反应管中进行。可以将3g的催化剂的样品置于小室中,并且可以在30cc/min的氦惰性气体的连续流动中加热至800K,用于表面脱气。然后,可以在氦气气氛中将该小室冷却至室温,并且可以将流转换至探测气体(O2或CO2),以使得其在室温下在表面上吸附约30分钟。可以以30cc/min的流动速率将氦气流再次引入约30分钟。然后可以开始温度程序,并且可以以1K/s的加热速率在273和800K之间的温度获得TPD光谱。
可以使用高分辨率透射电子显微镜(TEM)研究金属金颗粒在催化剂的表面上的排列和尺寸分布。可以使用TEM,使用以下式d=Σnidi/Σni计算平均粒径d,其中ni是直径di的颗粒的数量(Kozlov et al.)。选择大约300个颗粒以确定金颗粒的平均直径。可以对合成的和使用的催化剂记录TEM以研究反应条件对金属金的分布和粒径的影响。由于多相催化反应发生在固体催化剂的表面,并且产物形成的速率是负载催化剂的表面积的函数,因此表面积是重要的。可以使用常规的Brunauer-Emmett-Teller(BET)多层氮吸附方法获得催化剂的总表面积。固态31P核磁共振NMR是用于膦复合物表征的最有价值的光谱技术中的一种。31P化学位移和1J Au-P耦合常数可以受配位至膦原子的配体的圆锥角和电负性的影响。(Silva et al.,Vibrational and Solid State(CP/MAS)31P NMR Spectroscopic Studiesof Bis(trimethylphosphine)Gold(I)Halides,Journal of Molecular Structure(2000);516:263)。可以记录单独的三烷基膦配体,金(I)硝酸盐前体复合物,以及负载金复合物的31P NMR光谱,其有助于由于金复合物与载体表面的化学相互相用的化学位移变化的研究。此外,值得记录吸附在载体上的PR3配体的31P NMR化学位移,并且将它们与负载金属复合物的那些比较,其帮助确定复合物在载体上的分解机理。可以在400MHz NMR谱仪上通过在室温下的固态交叉极化旋转(cross-polarization spinning),获得31P NMR谱。可以相对于85%H3PO4的外部参考标准测量31P配位化学位移(Δδ=δ复合物-δ配体)。
可以使用X射线光电子能谱(XPS)测量在热煅烧之前和之后金前体以及负载金前体的Au 4f、P 2p、和O 1s轨道的结合能。Au 4f结合能的位置的监测可以给出关于金的形式氧化态(formal oxidation state)的清晰显示。结合能的值可以反映载体表面上金的化学性质。约84.4ev的4f结合能对应于金属金,同时86.5ev和88.3ev之间的结合能归于离子金Au(Czanderna;Lin et al.,Gold Supported on Surface Acidity Modified Y-Type andIron/Y-type Zeolite for CO Oxidation,Applied Catalysis B(2002);36:19)。小于84ev的表面上金的4f结合能表示在载体表面上较大的金颗粒的形成。可以利用X射线粉末衍射技术(XRD)监测在热煅烧之后载体上的金属金颗粒的形成。这可以通过观察在2θ=44.4°处的Au(200)峰以及2θ=38.2°处的Au(111)值实现(Yuan et al.,(1997)。Au(111)衍射峰的锐度和强度给出了关于载体的表面上的金颗粒的尺寸的指示。峰越锐且越强,金的晶体尺寸越大。可以使用X射线衍射仪用Cu Ku辐射在10°-80°的2θ范围内记录XRD图案。
可以致力于生长适合于X射线分析的叔三烷基膦金(I)硝酸盐复合物的单晶。晶体结构的测量可以用于评估金属-金属闭壳层分子间相互作用(Mathieson et al.,TheSolid State Aggregation of Two Gold(I)Nitrate Complexes,Journal of ChemicalSociety,Dalton Transaction(2000);3881)。这种相互相用强烈地取决于与配位于膦原子的烷基配体的性质,如电负性和空间效应。这种类型的相互相用可以直接相关于负载金复合物的热解时形成的金属金的分散性和粒径。可以使用原子力显微(AFM)以研究载体表面上的金复合物沉积前后的表面形态。此外,可以通过收集在不同的煅烧温度下的样品的形貌图来研究煅烧温度的影响。这种类型的分析可以给出关于金属颗粒易于凝聚程度的印象(Ken-ichi et al.,Atomic Force Microscopy Study on Thermal and UV-IrradiativeFormation and Control of Au Nana-particles on TiO2(110)From Au(PPh3)(NO3),Journal of Physical Chemical Physics(2001);3:3871)。由柱状图可以计算在每个煅烧温度下的粒径分布和高度分布。可以在AFM室内在干燥空气的流下完成样品的热解。
用于乙烯环氧化的反应器系统
用于在负载金纳米颗粒催化剂的存在下氧化乙烯至环氧乙烷的反应器系统可以是适合于提供气相、液相和固相之间充分接触的任何类型,如固定床流动反应器、泡罩塔反应器(bubble column reactor)、具有固定的或分散的乙烯注入的浆料搅拌的釜式反应器等。在一个实施方式中,在固定床流动反应器中进行乙烯至环氧乙烷的选择性氧化。在一个实施方式中,在固定床流动反应器中进行氧化乙烯至环氧乙烷。图5显示了通过使用本公开主题的负载金纳米颗粒催化剂用于氧化乙烯至环氧乙烷的示例性反应器系统1。
在一个非限制性实施例中,如在图5中示出的,将具有约1cm的内径的不锈钢固定床反应器管2以约10cm的固定床长度填充有本公开主题的负载金纳米颗粒催化剂。将反应器管2用装备有热电偶4和5(以测量在每个部分中的温度)的三加热区炉3覆盖。将另一个热电偶6在催化剂床7的中心处置于反应器管2内侧。反应混合物的气体反应物包含乙烯15和氧气16。此外,在一些实施方式中,气体混合物包含惰性气体17。在一个实施方式中,惰性气体是氩气。在反应为放热时,惰性气体起热量移除剂的作用。惰性气体不影响催化剂性能。在引入反应器系统之前将气体反应物混合。在气体反应物混合物进入反应器管2之前,在预加热器8处,将其预加热至约100℃至约180℃的温度。另外地和可替代地,可以将气体反应物单独预加热。将反应器系统1装备有用于所有气体反应物的质量流量控制器9、10、11和12以监控气体在它们进入预加热器8之前的流动速率。反应器系统1包括连接在反应器管2的出口之后的背压调节器13以控制反应压力。通过气体反应物的进料初始提供反应压力,并且在反应已经开始之后,通过使用背压调节器13保持反应压力。反应压力可以是约10巴至约25巴。在一些实施方式中,反应压力可以是约15巴至约22巴。如在图5中示出的,反应器管2还包括压力计18、防爆片(rupture disk)19、四个止回阀(check valve)20-23和四个过滤器24-27。
所有的连接反应器至气相色谱仪14的管道覆盖有可以加热至130℃的加热带以防止产物在管道中的任何凝结。在装备有火焰电离检测器(FID)和热传导检测器(TCD)的Hewlett-Packard 6890仪器中进行反应物进料和产物气体的气相色谱(GC)分析。GC炉温和可以配备有1mL的样品环的注射口在150℃下运行。将包含环氧乙烷、乙烯、氮气、氧气、一氧化碳、氩气和二氧化碳的合适的校准气体混合物用于GC的校准并且用于测定每种气体的响应因子(response factor)。对于其他期望的液体产物,如乙醛、乙酸和甲醛,可以制备标准溶液用于GC校准。
通过将催化剂床置于具有置于加热至期望的反应温度的炉中的壁的反应管之内来提供反应温度。用于氧化乙烯至环氧乙烷的反应温度可以是约160℃至约220℃。在一些实施方式中,反应温度是约180℃至约200℃。
通过应用适当的测量,可以广泛地改变进料气体混合物中的氧浓度,从进料混合物的约0.1%至约50%或更高,以避免爆炸问题。氧可以来自空气或纯氧来源。在一个实施方式中,空气是进料中的氧的来源。
可以根据下列等式1和2计算乙烯转化率和产物选择性:
其中Cj是组分j的摩尔分数,等式3的产率是转化率和选择性相乘的结果:
制备参数的影响
包括载体的类型和/或性质、金前体、pH值、金浓度和碱性促进剂的各种制备参数可以影响负载金纳米颗粒催化剂的催化活性和选择性。在反应条件和金浓度的标准设置下,可以以四个阶段评估制备参数的影响。在第一阶段中,确定用于由金属盐沉淀载体氢氧化物的最佳pH值。在一个实施方式中,该pH值是约5至约10。这可以在负载特定的三烷基膦金(I)硝酸盐复合物之前对所有的载体完成。可以通过使用10%的氢氧化钾溶液调节pH值。在第二阶段中,研究了载体以及载体和金复合物之间的化学相互作用的性质的影响。在这个阶段中,在固定的金加载下将所有的金复合物负载在每种氧化物载体上并且在固定的反应条件下评估。第三阶段确定适当的金载量。在一个实施方式中,本公开主题的负载金纳米颗粒催化剂包含约0.1%wt%至约5wt%(例如,约0.2wt%至约5wt%)的硝基(磷化合物)金(I)复合物(例如,硝基(三烷基膦)金(I)复合物)。在第四阶段中,确定碱性促进剂对负载金纳米颗粒催化剂的催化活性和选择性的影响。在一个实施方式中,碱性促进剂是铯。在添加至载体之前可以以不同的浓度将硝酸铯引入金复合物的溶液。
机理和动力学
本文中公开的负载金纳米颗粒催化剂展现出用于乙烯环氧化的优异的催化活性和选择性,并且可以用于研究反应动力学和机理。可以使用固定的金加载、固定的床长度、和固定的反应压力进行所有的动力学分析。乙烯和氧的转化率可以保持在10%水平或更低。可以进行多组分析以研究反应机理。首先是研究在固定的反应条件下反应物分压对反应速率的影响。每种反应物的浓度可以在约1%至约15%的范围内改变,同时其他反应物的浓度可以保持在约15%。可以通过氩气的流调节总流动速率。这可以最终有助于确定速率常数k以及相对于每种反应物反应的级数(order)以及反应的总级数(overall order)。
第二组的分析是评估气体在催化剂床上的接触时间对反应速率和催化剂选择性的影响。这可以通过在固定的反应物组成和固定的反应条件下在约50ml/min至约300ml/min的范围内总流动速率的变化实现。
第三组的分析是检验在约50℃至300℃的范围内的反应温度对反应速率和乙烯转化率的影响。此外,可以由Arrhenius等式直接计算表观活化能。图6显示了在由本公开主题的方法合成的负载金纳米颗粒催化剂上乙烯至环氧乙烷的选择性氧化的一种机理。如在图7A和7B中示出的,另一种机理表明化学吸附在表面上的原子氧是乙烯选择性环氧化的活性相,或者乙烯与氧化学吸附在表面上并且根据Langmuir-Hinshelwood机理在表面上反应。
术语“约”或“基本上”是指在由本领域中的普通技术人员测定的具体值的可接受的误差范围之内,其将部分取决于该值是如何测量或确定的,即,测量系统的限制。例如,“约”可以是指给定值的最高达20%、最高达10%、最高达5%、和或最高达1%的范围。
如在本文中使用的,“烷基”指的是包含1-20个碳原子的饱和或不饱和的烃,包括非环和环状结构(如环己烷等)两者。示例性的烷基包括但不限于,甲基、乙基、丙基、异-丙基(i-propyl)、异丙基(isopropyl)、丁基、叔丁基、异丁基、仲丁基、戊基、己基、环丙基、环丁基、环戊基、环己基、丙烯基、丁烯基、和环己烯基。键连的二价烷基基团被称为“亚烷基”,包括但不限于,亚乙基和亚丙基。
如在本文中使用的,术语“芳基”指的是单环或多环的(例如,具有2、3或4个稠环)芳族烃。示例性的芳基包括但不限于,苯基、萘基、蒽基、菲基、茚满基和茚基。在一些实施方式中,芳基基团具有6至约20个碳原子、6至约15个碳原子、或6至约10个碳原子。
如在本文中所使用的,术语“芳烷基”指的是被芳基取代的烷基。芳烷基的一个实例是苄基。
根据本公开的主题,所有以下描述的“烷基”、“芳基”、和“芳烷基”可以是可选地取代的。如在本文中使用的,术语“取代的”是指基团进一步地被选自以下的一种或更多种基团取代:氧、氮、硫、烷基、烯基、炔基、芳基、卤素、卤代烷基、卤代烯基、卤代炔基、卤代芳基、羟基、烷氧基、烯氧基、炔氧基、芳氧基、羧基、苄氧基、卤代烷氧基、卤代烯氧基、卤代炔氧基、卤代芳氧基、硝基、硝基烷基、硝基烯基、硝基炔基、硝基芳基、硝基杂环基、叠氮基、氨基、烷基氨基、烯基氨基、炔基氨基、芳基氨基、苄基氨基、酰基、烯基酰基、炔基酰基、芳基酰基、酰氨基、酰氧基、醛基、烷基磺酰基、芳基磺酰基、烷基磺酰基氨基、芳基磺酰基氨基、烷基磺酰氧基、芳基磺酰氧基、杂环基、杂环氧基、杂环基氨基、卤代杂环基、烷基亚磺酰基(alkylsulphenyl)、芳基亚磺酰基(arylsulphenyl)、羰基烷氧基、羰基芳氧基、巯基、烷硫基、芳硫基、酰硫基等,具有1至20个碳原子。
尽管已经详细地描述了本公开主题和其优点,但应当理解的是,在没有违背如通过所附权利要求限定的本公开主题的精神和范围的情况下,本文中可以进行各种的改变、替换和变更。此外,本公开主题的范围并不旨在受限于在说明书中描述过程、器械、制造、和物质组成、方式、方法和步骤的具体实施方式。由本公开主题的公开内容,本领域普通技术人员将易于理解,根据本公开的主题可以利用进行与本文描述的相应实施方式基本相同的功能或实现基本相同的结果的目前存在的或之后有待开发的过程、器械、制造、物质组成、方式、方法或步骤。因此,所附的权利要求旨在包括这类修改在它们的范围内。
Claims (20)
1.一种用于制备负载金纳米颗粒催化剂的方法,所述方法包括:
将磷化合物的溶液添加至氯(二甲基硫醚)金(I)的溶液以获得氯(磷化合物)金(I)复合物的溶液,
其中,所述磷化合物选自由以下各项组成的组:具有式PR1R2R3的膦、具有式P(OR4)R5R6的次膦酸酯、具有式P(OR7)(OR8)R9的亚膦酸酯、具有式P(OR10)(OR11)(OR12)的亚磷酸酯、或包括上述至少一种的组合;并且
其中,R1至R12各自独立地是烷基、取代的烷基、芳基、取代的芳基、芳烷基、取代的芳烷基、或包括上述至少一种的组合;
将所述氯(磷化合物)金(I)复合物的溶液添加至硝酸银的溶液以获得硝基(磷化合物)金(I)复合物的溶液;
将所述硝基(磷化合物)金(I)复合物的溶液施加至金属氢氧化物载体;
干燥所述金属氢氧化物载体;以及
锻烧干燥的所述金属氢氧化物载体以形成所述负载金纳米颗粒催化剂。
2.根据权利要求1所述的方法,其中,所述金属氢氧化物是氢氧化铝、氢氧化镁、氢氧化锌、氢氧化铁、氢氧化镍、氢氧化钛、或包括上述至少一种的组合。
3.根据权利要求1至2中任一项或多项所述的方法,其中,所述金属氢氧化物是通过水解氢氧化钾溶液中的金属获得的。
4.根据权利要求2所述的方法,其中,所述金属氢氧化物是氢氧化钛。
5.根据权利要求4所述的方法,其中,所述氢氧化钛是通过水解氢氧化钾溶液中的四异丙醇钛获得的。
6.根据权利要求3或5所述的方法,其中,所述水解在约5至约10的pH值下进行。
7.根据权利要求6所述的方法,其中,通过添加所述氢氧化钾溶液调节pH值。
8.根据权利要求1至7中任一项或多项所述的方法,其中,在连续搅拌约12小时下将所述硝基(磷化合物)金(I)复合物的溶液施加至所述金属氢氧化物。
9.根据权利要求1至8中任一项或多项所述的方法,其中,在真空下在约20℃至约25℃的温度下将所述金属氢氧化物干燥。
10.根据权利要求1至9中任一项或多项所述的方法,其中,在约100℃至约300℃的温度下,煅烧干燥的所述金属氢氧化物。
11.根据权利要求1至10中任一项或多项所述的方法,其中,所述方法是在惰性氮气气氛中进行的。
12.根据权利要求1至11中任一项或多项所述的方法,进一步包括,在将所述硝基(磷化合物)金(I)复合物的溶液施加至所述金属氢氧化物载体之前,将碱性促进剂添加至所述硝基(磷化合物)金(I)复合物的溶液。
13.根据权利要求12所述的方法,其中,所述碱性促进剂是铯。
14.根据权利要求1至13中任一项或多项所述的方法,其中,所述磷化合物是所述式PR1R2R3的膦。
15.根据权利要求1至14中任一项或多项所述的方法,其中
所述烷基是异丙基、环己基、叔丁基、乙基、或包括上述至少一种的组合;
所述芳基是苯基;
所述取代的芳基是均三甲苯基、2,6-二甲氧基苯基、4-甲氧基苯基、l-萘基、4-甲基苯基、或包括上述至少一种的组合;并且
所述芳烷基是苄基。
16.一种通过权利要求1至15中任一项或多项所述的方法制备的负载金纳米颗粒催化剂。
17.根据权利要求16所述的负载金纳米颗粒催化剂,其中,所述金纳米颗粒的尺寸是约2nm至约15nm。
18.根据权利要求16或权利要求17所述的负载金纳米颗粒催化剂,包含按重量计约0.2%至约5%的所述硝基(磷化合物)金(I)复合物。
19.一种用于将乙烯氧化成环氧乙烷的方法,包括在权利要求16至18中任一项或多项所述的负载金纳米颗粒催化剂的存在下使乙烯和氧反应。
20.根据权利要求19所述的方法,其中,所述方法在固定床流动反应器中进行,可选地其中,将惰性气体进料至氧化过程。
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