CN110215919B - 一种高分散负载型催化剂及其制备方法和应用 - Google Patents
一种高分散负载型催化剂及其制备方法和应用 Download PDFInfo
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- CN110215919B CN110215919B CN201910451496.7A CN201910451496A CN110215919B CN 110215919 B CN110215919 B CN 110215919B CN 201910451496 A CN201910451496 A CN 201910451496A CN 110215919 B CN110215919 B CN 110215919B
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- tannic acid
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- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
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- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
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- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
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Abstract
本发明公开了一种高分散负载型催化剂的制备方法,包括:将单宁酸、载体加入到活性金属前驱体溶液中,调节pH至8~11,反应1~3h后过滤干燥,然后还原得到高分散负载型催化剂。由于单宁酸的鳌合和稳定作用,使载体普适性强,不再限于具有缺陷的氧化物载体。上述方法简单有效、原料易得、价格低廉,有重要的工业应用前景。本发明还公开了一种上述方法制备得到的高分散负载型催化剂,催化剂中活性金属分散度高,原子利用率高。本发明还公开了一种所述高分散负载型催化剂在烯烃氢甲酰化反应和不饱和烃氢酯基化反应中的应用,催化效率高,选择性好,与传统均相催化剂相比,易于从氢甲酰化反应体系和氢酯基化反应体系中分离,降低回收成本。
Description
技术领域
本发明涉及催化剂技术领域,具体涉及一种高分散负载型催化剂及其制备方法和应用。
背景技术
氢甲酰化反应是利用烯烃和合成气(CO和H2)为原料在催化剂作用下合成醛的过程。氢甲酰化反应的产物醛类化合物是高附加值精细化学品,广泛应用于香料、汽油添加剂、树脂和表面活性剂等化工产品的制备。自1938年Otto Roelen教授发现该反应以来,氢甲酰化反应已成为当今工业应用中最重要的化学反应之一。
氢甲酰化反应催化剂的发展目前已经历了四代,前两代是基于羰基钴的催化体系,此类催化剂最大的难题在于对反应压力及反应温度要求高,要求反应压力20~30MPa,反应温度150~200℃。相对而言,第三代油溶性羰基铑膦催化剂的出现使得氢甲酰化反应能够在低温、低压的温和条件下进行,反应温度110±10℃,反应压力1.6~3.5MPa,有效降低了反应设备的投资和能耗,但只适用于短链烯烃的氢甲酰化反应,此类催化剂在用于长链烯烃的氢甲酰化反应时出现了铑催化剂回收困难的问题。由于铑金属价格昂贵,其回收再利用对生产成本有至关重要的影响。第四代催化剂为水溶性铑膦催化剂,采用油-水两相反应体系,可将产物与催化剂有效分离,解决了长链烯烃氢甲酰化过程中催化剂的回收问题。
公开号为CN107537481A的专利说明书公开了一种负载型单原子铑基催化剂制备及其在烯烃氢甲酰化反应中的应用。催化剂主要活性组分为铑,载体为纳米氧化锌。铑在载体上以原子级别分散,铑含量为催化剂总质量的0.005~2wt%。该催化剂在烯烃氢甲酰化反应中表现出较高的催化活性和稳定性,最佳反应条件下,目标产物最高收率为90%,仍然有待提高。
烯烃或炔烃的氢酯基化反应,是利用烯烃或炔烃,与一氧化碳(CO)和醇类为原料在催化剂作用下生成酯类化合物的过程。脂肪酸酯是一类极为重要的化合物,是制备增塑剂、洗涤剂、润滑剂等化学品的重要中间体,在精细化工领域具有举足轻重的地位。典型地,丙酸甲酯(MP)是制备甲基丙烯酸甲酯(MMA)的前驱体,而MMA是合成广泛应用的透明热塑性塑料-聚甲基丙烯酸甲酯(PMMA)的原料。MP可由乙烯、甲醇和CO经过氢甲酯化反应得到。
目前,氢酯基化反应的催化剂绝大多数为Pd基的均相催化剂。此类催化剂一般在膦配体和酸性助催化剂存在下才能起作用。例如,Jiro Tsuji等人报道了利用PdCl2/HCl催化体系合成羰基酸酯(Tetrahedron Lett.,1963,4,1437)。Cristina Jiménez-Rodriguez等人报道了一种催化不饱和酸或酯的氢甲酯化反应制备α,ω-二羰基酸酯的Pd基均相催化剂(Inorg.Chem.Commun.,2005,8,878)。Eduardo J.García-Suárez等人报道了一种含Pd的催化体系,用于催化乙烯的氢甲酯化反应制备MP(Green Chem.,2014,16,161)。Haoquan Li等人含卤素的Pd基催化剂,用于催化各类烯烃制备支链酯(Nat.Chem.,2016,8,1159)。虽然这类催化剂具有较高的活性和选择性,但反应后很难将贵金属回收再利用,导致生产成本高。
因此开发具有高活性的非均相催化剂对于氢酯基化过程具有重要的实际意义。Jinghua An等人报道了CeO2担载的Ru纳米团簇用于乙烯的氢甲酯化反应用于制备MP,发现在不需要磷配体的情况下Ru/CeO2催化剂依然能表现出优异的MP选择性。但由于催化剂中Ru颗粒较大,分散度较低,从而导致催化剂的活性较低(J.Am.Chem.Soc.,2018,140,4172)。
发明内容
针对本领域存在的不足之处,本发明提供了一种高分散负载型催化剂的制备方法,由单宁酸辅助分散制备得到高分散负载型催化剂,催化剂的核心——活性金属呈现单原子分散状态,其对烯烃的氢甲酰化反应、不饱和烃的氢酯基化反应具有优异的催化活性及稳定性,该制备方法原料廉价易得、操作简单。
一种高分散负载型催化剂的制备方法,包括:将单宁酸、载体加入到活性金属前驱体溶液中,调节pH至8~11,反应1~3h后过滤干燥,然后还原得到高分散负载型催化剂。
所述活性金属选自Rh、Pd和Ru中的至少一种。
活性金属前驱体、单宁酸和载体在合适pH的溶液中分散,由于制备过程中单宁酸的鳌合和稳定作用,催化剂中活性金属离子以原子级状态分布于载体上,还原后形成单位点催化剂。
在所述催化剂制备中,单宁酸在适当的pH范围与活性金属形成强络合作用以分散活性金属离子。同时单宁酸富含羟基,与载体中氧原子等富电原子形成强氢键,将整个络合基团稳定于载体表面。由于单宁酸的限域作用,在还原过程中活性金属原子不会团聚,只能在原位置被还原,从而形成单原子催化剂。
所述单宁酸的分子式如下式(I)所示:
所述活性金属前驱体选自活性金属的卤化物、硝酸盐、乙酰丙酮盐、醋酸盐、氯铑酸盐、氯钯酸盐和氯钌酸盐中的至少一种。
所述载体为多孔炭材料或含有Si、Al、Ti、Zr、Ce、Mo、W、V、Mg、Ca、Cr、Mn、Fe和Zn中的一种或多种元素的金属氧化物。
采用Na2CO3、NaHCO3、NaOH和NH3·H2O中的一种或多种调节pH。
优选地,所述单宁酸与活性金属前驱体的质量比为0.1~50:1,单宁酸过少起不到络合活性金属的作用,单宁酸过多会将活性金属完全包埋,无法起到催化作用。更优选地,所述单宁酸与活性金属前驱体的质量比为1~20:1。此比例下更有利于活性金属的分散和催化效果的提高。
优选地,所述载体与活性金属前驱体中的铑的质量比为0.25~10000:1。更优选地,所述载体与活性金属前驱体中的铑的质量比为9~10000:1。金属含量过低,催化效率低,金属含量过高,无法有效分散金属。
所述的还原可为液相还原或气相还原。
所述的液相还原的还原剂为柠檬酸钠、乙二醇、硼氢化钠、水合肼、四丁基硼氢化物和甲酸钠中的一种或多种。
所述的气相还原的还原性气氛为H2、H2/Ar、H2/He或H2/N2。
当所述活性金属为Rh时,所述的气相还原的温度为50~250℃,使Rh能够还原,且单宁酸不至于分解过快而导致金属团聚。
当所述活性金属为Pd和/或Ru,气相还原的温度为50~500℃,适合Pd和Ru的还原,且单宁酸不至于分解过快而导致金属团聚。
本发明还提供了一种所述的高分散负载型催化剂的制备方法制备得到的高分散负载型催化剂。
所述的高分散负载型催化剂中活性金属以单原子状态分散在载体表面。
在一优选例中,所述的高分散负载型催化剂中活性金属的质量百分含量为0.01%~10%
在另一优选例中,所述的高分散负载型催化剂中活性金属的质量百分含量为3%~10%。
本发明还提供了一种所述的高分散负载型催化剂在烯烃氢甲酰化反应中的应用,所述的活性金属为Rh。
所述的烯烃氢甲酰化反应可在高压反应釜中进行。
所述的烯烃氢甲酰化反应的原料包括H2、CO和烯烃,所述烯烃溶于溶剂中。
所述的烯烃可以为端烯烃或中间烯烃,也可为双烯烃,如1-丁烯、2-戊烯、1-辛烯、2-丁烯、2-己烯、2-辛烯,1,4-丁二烯等。
优选地,所述的烯烃选自C2~C18的烯烃。
所述的溶剂为苯、甲苯、二甲苯、三甲苯、氯仿、二氯甲烷、四氢呋喃、1,4-二氧六环、二甲基亚砜或乙腈中的一种或多种。
所述的烯烃氢甲酰化反应的反应条件为:H2和CO摩尔比1:1,反应温度为40~150℃,反应压力为0.5~3MPa,所述烯烃与高分散负载型催化剂中的铑的摩尔比为100~10000:1。
本发明还提供了一种所述的高分散负载型催化剂在氢酯基化反应中的应用。
所述的氢酯基化反应可在高压反应釜中进行。
所述的氢酯基化反应的原料包括脂肪醇、CO和不饱和烃,所述不饱和烃为烯烃或炔烃。
所述不饱和烃可以为端烯烃、中间烯烃、端炔烃和中间炔烃,也可为双烯烃和双炔烃,如1-丁烯、1-丁炔、2-戊烯、1-辛烯、2-丁烯、2-丁炔、2-辛烯,1,4-丁二烯等。
优选地,所述不饱和烃选自C2~C18的不饱和烃。
所述氢酯基化反应可以在无溶剂下进行,也可以在反应溶剂存在的条件下进行。
所述的反应溶剂选自水、苯、甲苯、二甲苯、三甲苯、氯仿、二氯甲烷、四氢呋喃、1,4-二氧六环、二甲基亚砜和乙腈中的至少一种。
所述的氢酯基化反应的反应条件为:反应温度为40~250℃,反应总压为0.5~5.0MPa,所述不饱和烃与氢酯基化反应催化剂中活性金属的摩尔比为1000~50000:1。
本发明与现有技术相比,主要优点包括:
(1)方法简单有效、原料易得、价格低廉,具有重要的工业应用前景。
(2)活性金属分散度高,原子利用率高。
(3)载体普适性强:由于单宁酸的鳌合和稳定作用,单原子催化剂的载体不再限于具有缺陷的氧化物载体。
(4)与传统均相催化剂相比,催化剂易于从氢甲酰化反应体系进和氢酯基化反应体系中分离,降低回收成本。
附图说明
图1为实施例2的高分散负载型催化剂的透射电镜照片,白色圆圈用于指出单原子铑的分布位置;
图2为实施例8的高分散负载型钯催化剂的透射电镜照片,白色圆圈用于指出单原子钯的分布位置;
图3为应用例5的催化剂经12次套用的活性数据图。
具体实施方式
下面结合附图及具体实施例,进一步阐述本发明。应理解,这些实施例仅用于说明本发明而不用于限制本发明的范围。下列实施例中未注明具体条件的实验方法,通常按照常规条件,或按照制造厂商所建议的条件。
实施例1
称取20mg(NH4)3RhCl6溶于20mL水中,加入1g活性炭,搅拌0.5h后,加入300mg单宁酸,继续搅拌0.5h,逐滴加入1M的NaOH溶液直至溶液pH=11,继续反应2h,过滤、洗涤至滤液中性,置于70℃下干燥24h。烘干后粉体置于流速50mL/min的H2/Ar(体积比1:5)混合气氛,160℃还原1h得到高分散负载型催化剂。
实施例2
称取20mg RhCl3·3H2O溶于20mL水中,加入1g活性炭,搅拌0.5h后,加入300mg单宁酸,继续搅拌0.5h,逐滴加入1M的NaOH溶液直至溶液pH=10,继续反应2h,过滤、洗涤至滤液中性,置于70℃下干燥24h。烘干后粉体置于流速50mL/min的H2/Ar(体积比1:5)混合气氛,160℃还原1h得到高分散负载型催化剂。
如图1所示,本实施例的高分散负载型催化剂中的铑原子以单原子形式存在。
实施例3
称取50mg RhCl3·3H2O溶于20mL水中,加入1g活性炭,搅拌0.5h后,加入300mg单宁酸,继续搅拌0.5h,逐滴加入1M的NaOH溶液直至溶液pH=9,继续反应2h,滴加0.1M NaBH4还原Rh离子,过滤、洗涤至滤液中性,置于70℃下干燥24h得到得到高分散负载型催化剂。
实施例4
称取200mg RhCl3·3H2O溶于40mL水中,加入1g活性炭,搅拌0.5h后,加入600mg单宁酸,继续搅拌0.5h,逐滴加入1M的NaOH溶液直至溶液pH=9,继续反应2h,过滤、洗涤至滤液中性,置于70℃下干燥24h。烘干后粉体置于流速50mL/min的H2/Ar(体积比1:5)混合气氛,200℃还原1h得到高分散负载型催化剂。
实施例5
称取20mg RhCl3·3H2O溶于20mL水中,加入1g CeO2,搅拌0.5h后,加入300mg单宁酸,继续搅拌0.5h,逐滴加入1M的NaOH溶液直至溶液pH=8,继续反应2h,过滤、洗涤至滤液中性,置于70℃下干燥24h。烘干后粉体置于流速50mL/min的H2/Ar(体积比1:5)混合气氛,160℃还原1h得到高分散负载型催化剂。
实施例6
称取20mg RhCl3·3H2O溶于20mL水中,加入1g CeO2,搅拌0.5h后,加入300mg单宁酸,继续搅拌0.5h,逐滴加入1M的NaOH溶液直至溶液pH=9,继续反应2h,过滤、洗涤至滤液中性,置于70℃下干燥24h。烘干后粉体置于流速50mL/min的H2/Ar(体积比1:5)混合气氛,200℃还原1h得到高分散负载型催化剂。
应用例1催化丙烯氢甲酰化反应
采用实施例2中制备的高分散负载型催化剂。具体反应条件为:采用100mL高压反应釜,加入催化剂50mg、甲苯10mL、丙烯0.4MPa、CO0.8MPa、H2 0.8MPa,反应温度100℃,反应时间6h。经测试,丙烯转化率为97%,正丁醛选择性为96%,正丁醛/异丁醛的摩尔比为26。
应用例2催化苯乙烯氢甲酰化反应
采用实施例2中制备的高分散负载型催化剂。具体反应条件为:采用100mL高压反应釜,加入催化剂50mg、甲苯10mL、苯乙烯5mmol、CO 0.8MPa、H2 0.8MPa,反应温度100℃,反应时间6h。经测试,苯乙烯转化率为98%,醛类选择性为98%,苯丙醛/2-苯基丙醛的摩尔比为15。
应用例3催化苯乙烯氢甲酰化反应
采用实施例3中制备的高分散负载型催化剂。具体反应条件为:采用100mL高压反应釜,加入催化剂100mg、甲苯10mL、苯乙烯5mmol、CO 0.8MPa、H2 0.8MPa,反应温度100℃,反应时间3h。经测试,苯乙烯转化率为98%,醛类选择性为98%,苯丙醛/2-苯基丙醛比例为16。
应用例4催化异丁烯氢甲酰化反应
采用实施例2中制备的高分散负载型催化剂。具体反应条件为:采用100mL高压反应釜,加入催化剂50mg、甲苯10mL、异丁烯0.8MPa、CO 0.8MPa、H2 0.8MPa,反应温度100℃,反应时间6h。经测试,异丁烯转化率为98%,异戊醛选择性为97%。
实施例7
称取20mg PdCl2溶于20mL水中,加入1g氮掺杂多孔炭,搅拌0.5h后,加入300mg单宁酸,继续搅拌0.5h,逐滴加入1M的NaOH溶液直至溶液pH在10左右,继续反应2h,过滤、洗涤至滤液中性,置于70℃下干燥24h。烘干后粉体置于流速50mL/min的H2/Ar(体积比1:5)混合气氛,120℃还原1h得到高分散负载型钯催化剂。
实施例8
称取20mg PdCl2溶于20mL水中,加入1g活性炭,搅拌0.5h后,加入300mg单宁酸,继续搅拌0.5h,逐滴加入1M的NaOH溶液直至溶液pH在10左右,继续反应2h,过滤、洗涤至滤液中性,置于70℃下干燥24h。烘干后粉体置于流速50mL/min的H2/Ar(体积比1:5)混合气氛,120℃还原1h得到高分散负载型钯催化剂。
如图2所示,本实施例的高分散负载型钯催化剂中的钯原子以单原子形式存在。
实施例9
称取20mg Na2PdCl4溶于20mL水中,加入1g活性炭,搅拌0.5h后,加入300mg单宁酸,继续搅拌0.5h,逐滴加入1M的NaOH溶液直至溶液pH在10左右,继续反应2h,过滤、洗涤至滤液中性,置于70℃下干燥24h。烘干后粉体置于流速50mL/min的H2/Ar(体积比1:5)混合气氛,120℃还原1h得到高分散负载型钯催化剂。
实施例10
称取10mg RuCl3·3H2O溶于20mL水中,加入1g氮掺杂多孔炭,搅拌0.5h后,加入300mg单宁酸,继续搅拌0.5h,逐滴加入1M的NaOH溶液直至溶液pH在10左右,继续反应2h,过滤、洗涤至滤液中性,置于70℃下干燥24h。烘干后粉体置于流速50mL/min的H2/Ar(体积比1:5)混合气氛,350℃还原4h得到高分散负载型钌催化剂。
实施例11
称取10mg RuCl3·3H2O溶于20mL水中,加入1g活性炭,搅拌0.5h后,加入300mg单宁酸,继续搅拌0.5h,逐滴加入1M的NaOH溶液直至溶液pH在10左右,继续反应2h,过滤、洗涤至滤液中性,置于70℃下干燥24h。烘干后粉体置于流速50mL/min的H2/Ar(体积比1:5)混合气氛,350℃还原4h得到高分散负载型钌催化剂。
实施例12
称取50mg RuCl3·3H2O溶于20mL水中,加入1g活性炭,搅拌0.5h后,加入300mg单宁酸,继续搅拌0.5h,逐滴加入1M的NaOH溶液直至溶液pH=10,继续反应2h,滴加0.1M NaBH4还原Ru离子,过滤、洗涤至滤液中性,置于70℃下干燥24h得到高分散钌催化剂。
实施例13
称取200mg RuCl3·3H2O溶于40mL水中,加入1g活性炭,搅拌0.5h后,加入400mg单宁酸,继续搅拌0.5h,逐滴加入1M的NaOH溶液直至溶液pH=10,继续反应2h,过滤、洗涤至滤液中性,置于70℃下干燥24h。烘干后粉体置于流速50mL/min的H2/Ar(体积比1:5)混合气氛,200℃还原1h得到高分散负载型钌催化剂。
实施例14
称取20mg(NH4)2RuCl6溶于20mL水中,加入1g TiO2,搅拌0.5h后,加入300mg单宁酸,继续搅拌0.5h,逐滴加入1M的NaOH溶液直至溶液pH在10左右,继续反应2h,过滤、洗涤至滤液中性,置于70℃下干燥24h。烘干后粉体置于流速50mL/min的H2/Ar(体积比1:5)混合气氛,350℃还原4h得到高分散负载型钌催化剂。
实施例15
称取20mg PdCl2溶于20mL水中,加入1g CeO2,搅拌0.5h后,加入300mg单宁酸,继续搅拌0.5h,逐滴加入1M的NaOH溶液直至溶液pH在10左右,继续反应2h,过滤、洗涤至滤液中性,置于70℃下干燥24h。烘干后粉体置于流速50mL/min的H2/Ar(体积比1:5)混合气氛,120℃还原1h得到高分散负载型钯催化剂。
应用例5乙烯氢甲酯化反应合成MP
采用实施例8中制备的高分散负载型钯催化剂。具体反应条件为:采用100mL高压反应釜,加入催化剂20mg、甲醇10mL、乙烯10mmol、CO 1.0MPa,反应温度150℃,反应时间6h。经测试,乙烯转化率为99%,MP选择性为97%,如图3所示,催化剂经历12次套用后无明显性能下降。
应用例6乙烯氢甲酯化反应合成MP
采用实施例10中制备的高分散负载型钌催化剂。具体反应条件为:采用100mL高压反应釜,加入催化剂50mg、甲醇10mL、乙烯10mmol、CO 1.0MPa,反应温度150℃,反应时间1h。经测试,乙烯转化率为99%,MP选择性为96%。
应用例7乙烯氢甲酯化反应合成MP
采用实施例9中制备的高分散负载型钯催化剂。具体反应条件为:采用100mL高压反应釜,加入催化剂25mg、甲醇20mL、乙烯40mmol、CO 3.0MPa,反应温度200℃,反应时间3h。经测试,乙烯转化率为99%,MP选择性为98%。
应用例8乙烯氢甲酯化反应合成MP
采用实施例10中制备的高分散负载型钌催化剂。具体反应条件为:采用100mL高压反应釜,加入催化剂25mg、甲醇20mL、乙烯40mmol、CO 3.0MPa,反应温度200℃,反应时间3h。经测试,乙烯转化率为99%,MP选择性为98%。
应用例9苯乙烯氢甲酯化反应
采用实施例8中制备的高分散负载型钯催化剂。具体反应条件为:采用100mL高压反应釜,加入催化剂20mg、甲醇10mL、苯乙烯10mmol、CO 1.0MPa,反应温度140℃,反应时间6h。经测试,苯乙烯转化率为97%,苯丙酸甲酯选择性为98%。
应用例10乙炔氢甲酯化反应
采用实施例8中制备的高分散负载型钯催化剂。具体反应条件为:采用100mL高压反应釜,加入催化剂20mg、甲醇10mL、乙炔10mmol、CO 1.0MPa,反应温度150℃,反应时间6h。经测试,乙炔转化率为98%,丙烯酸甲酯选择性为97%。
此外应理解,在阅读了本发明的上述描述内容之后,本领域技术人员可以对本发明作各种改动或修改,这些等价形式同样落于本申请所附权利要求书所限定的范围。
Claims (5)
1.一种单原子催化剂,其特征在于,制备方法包括:将单宁酸、载体加入到活性金属前驱体溶液中,调节pH至8~11,反应1~3h后过滤干燥,然后还原得到活性金属以单原子状态分散在载体表面的单原子催化剂;
所述活性金属选自Rh、Pd和Ru中的至少一种;
所述单宁酸与活性金属前驱体的质量比为0.1~50:1;
所述载体与活性金属的质量比为0.25~10000:1;
所述的还原为液相还原,液相还原的还原剂为柠檬酸钠、乙二醇、硼氢化钠、水合肼、四丁基硼氢化物和甲酸钠中的一种或多种;或,所述的还原为气相还原,气相还原的还原性气氛为H2、H2/Ar、H2/He或H2/N2;
所述活性金属为Rh,气相还原的温度为50~250℃;或,所述活性金属为Pd和/或Ru,气相还原的温度为50~500℃。
2.根据权利要求1所述的单原子催化剂,其特征在于,所述活性金属前驱体选自活性金属的卤化物、硝酸盐、乙酰丙酮盐、醋酸盐中的至少一种或者氯铑酸盐、氯钯酸盐和氯钌酸盐中的至少一种;
所述载体为多孔炭材料或含有Si、Al、Ti、Zr、Ce、Mo、W、V、Mg、Ca、Cr、Mn、Fe和Zn中的一种或多种元素的金属氧化物。
3.根据权利要求1或2所述的单原子催化剂,其特征在于,所述的单原子催化剂中活性金属的质量百分含量为0.01%~10%。
4.一种根据权利要求1~3任一所述的单原子催化剂在烯烃氢甲酰化反应中的应用,其特征在于,所述的活性金属为Rh。
5.一种根据权利要求1~3任一所述的单原子催化剂在氢酯基化反应中的应用,其特征在于,所述的活性金属为Pd和/或Ru。
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