CN111203279B - 一种三明治纳米材料ZIF-8@Au25@ZIF-67及其制备方法和应用 - Google Patents
一种三明治纳米材料ZIF-8@Au25@ZIF-67及其制备方法和应用 Download PDFInfo
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- 239000002086 nanomaterial Substances 0.000 title claims abstract description 20
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- 239000013154 zeolitic imidazolate framework-8 Substances 0.000 title claims abstract 17
- MFLKDEMTKSVIBK-UHFFFAOYSA-N zinc;2-methylimidazol-3-ide Chemical compound [Zn+2].CC1=NC=C[N-]1.CC1=NC=C[N-]1 MFLKDEMTKSVIBK-UHFFFAOYSA-N 0.000 title claims abstract 17
- 238000005810 carbonylation reaction Methods 0.000 claims abstract description 21
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 135
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 64
- 238000006243 chemical reaction Methods 0.000 claims description 59
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 54
- 239000000243 solution Substances 0.000 claims description 44
- 239000001569 carbon dioxide Substances 0.000 claims description 32
- 229910002092 carbon dioxide Inorganic materials 0.000 claims description 32
- 239000003054 catalyst Substances 0.000 claims description 31
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 30
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 30
- 238000003756 stirring Methods 0.000 claims description 25
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 22
- 230000006315 carbonylation Effects 0.000 claims description 19
- 239000002904 solvent Substances 0.000 claims description 18
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 15
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical class [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 15
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- 239000007788 liquid Substances 0.000 claims description 15
- 238000007789 sealing Methods 0.000 claims description 15
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- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical compound CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 claims description 14
- 238000001816 cooling Methods 0.000 claims description 13
- -1 aromatic alkynes Chemical class 0.000 claims description 12
- 150000001345 alkine derivatives Chemical group 0.000 claims description 11
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims description 6
- 229910001981 cobalt nitrate Inorganic materials 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 6
- 239000012621 metal-organic framework Substances 0.000 claims description 5
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- 239000002243 precursor Substances 0.000 claims description 4
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- NVLDSCWHEUSPCV-UHFFFAOYSA-N [Co++].CO.[O-][N+]([O-])=O.[O-][N+]([O-])=O Chemical compound [Co++].CO.[O-][N+]([O-])=O.[O-][N+]([O-])=O NVLDSCWHEUSPCV-UHFFFAOYSA-N 0.000 claims description 2
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- 239000002184 metal Substances 0.000 claims 1
- 229910052751 metal Inorganic materials 0.000 claims 1
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- 239000000463 material Substances 0.000 abstract description 10
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- 238000003786 synthesis reaction Methods 0.000 abstract description 3
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- 125000002355 alkine group Chemical group 0.000 abstract 1
- 239000010931 gold Substances 0.000 description 35
- UEXCJVNBTNXOEH-UHFFFAOYSA-N Ethynylbenzene Chemical group C#CC1=CC=CC=C1 UEXCJVNBTNXOEH-UHFFFAOYSA-N 0.000 description 26
- 239000000047 product Substances 0.000 description 20
- 239000012295 chemical reaction liquid Substances 0.000 description 13
- XMIIGOLPHOKFCH-UHFFFAOYSA-N 3-phenylpropionic acid Chemical compound OC(=O)CCC1=CC=CC=C1 XMIIGOLPHOKFCH-UHFFFAOYSA-N 0.000 description 9
- 239000002244 precipitate Substances 0.000 description 8
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 239000008367 deionised water Substances 0.000 description 6
- 229910021641 deionized water Inorganic materials 0.000 description 6
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 6
- 239000002253 acid Substances 0.000 description 5
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- KBIAVTUACPKPFJ-UHFFFAOYSA-N 1-ethynyl-4-methoxybenzene Chemical group COC1=CC=C(C#C)C=C1 KBIAVTUACPKPFJ-UHFFFAOYSA-N 0.000 description 3
- 239000003513 alkali Substances 0.000 description 3
- 238000006473 carboxylation reaction Methods 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 3
- 229910052737 gold Inorganic materials 0.000 description 3
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- JKANAVGODYYCQF-UHFFFAOYSA-N prop-2-yn-1-amine Chemical compound NCC#C JKANAVGODYYCQF-UHFFFAOYSA-N 0.000 description 3
- 238000001308 synthesis method Methods 0.000 description 3
- QXSWHQGIEKUBAS-UHFFFAOYSA-N 1-ethynyl-4-fluorobenzene Chemical group FC1=CC=C(C#C)C=C1 QXSWHQGIEKUBAS-UHFFFAOYSA-N 0.000 description 2
- NHUBNHMFXQNNMV-UHFFFAOYSA-N 2-ethynylpyridine Chemical group C#CC1=CC=CC=N1 NHUBNHMFXQNNMV-UHFFFAOYSA-N 0.000 description 2
- KSZVOXHGCKKOLL-UHFFFAOYSA-N 4-Ethynyltoluene Chemical group CC1=CC=C(C#C)C=C1 KSZVOXHGCKKOLL-UHFFFAOYSA-N 0.000 description 2
- XUJNEKJLAYXESH-REOHCLBHSA-N L-Cysteine Chemical compound SC[C@H](N)C(O)=O XUJNEKJLAYXESH-REOHCLBHSA-N 0.000 description 2
- 229910002668 Pd-Cu Inorganic materials 0.000 description 2
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- 238000005119 centrifugation Methods 0.000 description 2
- WWVWWECUZUPLCL-UHFFFAOYSA-N cyclopropyne Chemical compound C1C#C1 WWVWWECUZUPLCL-UHFFFAOYSA-N 0.000 description 2
- VXAWCKIQYKXJMD-UHFFFAOYSA-N ethynamine Chemical group NC#C VXAWCKIQYKXJMD-UHFFFAOYSA-N 0.000 description 2
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- GAZZTEJDUGESGQ-UHFFFAOYSA-N 1-ethynyl-4-nitrobenzene Chemical group [O-][N+](=O)C1=CC=C(C#C)C=C1 GAZZTEJDUGESGQ-UHFFFAOYSA-N 0.000 description 1
- KBDLTYNZHQRMQC-UHFFFAOYSA-N 2-(4-methoxyphenyl)propanoic acid Chemical compound COC1=CC=C(C(C)C(O)=O)C=C1 KBDLTYNZHQRMQC-UHFFFAOYSA-N 0.000 description 1
- DVXIRBTZXZKOPP-UHFFFAOYSA-N 3-(4-methylphenyl)prop-2-ynoic acid Chemical compound CC1=CC=C(C#CC(O)=O)C=C1 DVXIRBTZXZKOPP-UHFFFAOYSA-N 0.000 description 1
- PALVOZXUYYJTDL-UHFFFAOYSA-N 3-pyridin-2-ylprop-2-ynoic acid Chemical compound OC(=O)C#CC1=CC=CC=N1 PALVOZXUYYJTDL-UHFFFAOYSA-N 0.000 description 1
- 235000013878 L-cysteine Nutrition 0.000 description 1
- 239000004201 L-cysteine Substances 0.000 description 1
- 239000013177 MIL-101 Substances 0.000 description 1
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 239000007900 aqueous suspension Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
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- 229910052709 silver Inorganic materials 0.000 description 1
- 229910000033 sodium borohydride Inorganic materials 0.000 description 1
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Abstract
本发明公开了一种三明治纳米材料ZIF‑8@Au25@ZIF‑67及其制备方法和应用,该材料的分子式为ZIF‑8@Au25@ZIF‑67,以ZIF‑8为内核,中间层为Au25纳米团簇,最外层为ZIF‑67。本发明三明治材料的合成条件温和,不需要PVP等其他添加剂。该材料可用于催化末端炔羰基化反应,能有效转换CO2,具有较高的活性和稳定性,可保持高活性循环利用五次,具有很好的实用性。
Description
技术领域
本发明涉及一种三明治纳米材料ZIF-8@Au25@ZIF-67及其制备方法和应用,属于材料合成领域。
背景技术
利用可再生资源是解决日益严重的环境问题的有效途径。其中,二氧化碳是最容易获得的资源,它具有无毒、可再生和廉价的优点。因此,利用二氧化碳转化是绿色化学背景下的一个研究热点,可以在获得有机精细化学品的同时解决化石能源短缺和温室效应问题。
炔酸类衍生物是有机合成工业重要的中间体之一,广泛用于医药、塑料、香料和感光树脂等化工产品中,早在1942年,MarieReimer首先报道了苯丙炔酸的合成方法,后来杨增家等利用阳光引发,制备苯丙炔酸,但这些产率均不高,且反应过程不易控制。Zhang课题组,在2011年先是合成了一种不含过渡金属的催化剂,在120℃加热状态下使用2.5atm CO2和 1.2倍当量的Cs2CO3完成了苯乙炔的羧化过程。(Green Chem.2011,13,1275-1279)后又用无配体Ag(I)催化系统催化末端炔烃的羧化,在1mol%的AgI,1.5倍当量的Cs2CO3,50-60℃, CO2为2atm的条件下完成催化反应(Org.Lett.2011,13,2402-2405)。随后为了提高催化剂的稳定性,金属修饰的金属有机框架(MOF)得到了广泛的发展。Cheng课题组,在MIL-101里将Ag离子原位还原成Ag纳米颗粒得到Ag@MOL-101催化剂,在70mg,2.7mmol%的Ag,Cs2CO3(1.5倍当量),CO2(1.0atm),50℃,DMF(5mL),15h的反应条件下,对末端芳香炔进行羰基化反应(Angew.Chem.Int.Ed.2015,54,988-991)。该反应存在催化剂,碱和溶剂的用量大等不足。随后,Trivedi课题组合成Pd-Cu@MOL-101催化剂,在100mg,2wt%的Pd-Cu,在Cs2CO3(1.5倍当量),CO2(1.0atm),25℃,DMF(5mL),24h的温和条件下对苯乙炔羰基化为苯丙炔酸,(New J.Chem.,2016,40,3109)。虽然在催化剂用量上有所下降,但碱和溶剂的用量依然很大。Beletskaya课题组合成了CuNPs/Al2O3的催化剂,在Cu NP(0.0075mmol),炔(0.15mmol)在Cs2CO3(2.0倍当量),CO2(2.0atm),60℃,DMF(2mL),6or 16h的温和条件下对苯乙炔羰基化为苯丙炔酸(Catal Lett,2017,147,2570–2580),但该反应还存在CO2压力大,碱和溶剂的用量大等缺点。
发明内容
本发明针对上述现有技术所存在的问题,提供了一种三明治纳米材料 ZIF-8@Au25@ZIF-67及其制备方法和应用。本发明设计合成的三明治纳米材料催化剂 ZIF-8@Au25@ZIF-67,外层为ZIF-67,其具有高稳定性,高孔隙率和有机功能,能够催化,分离,固载和活化气体(J.CO Util.2017,20,282-291),另外,外层ZIF-67的厚度直接影响催化反应。与文献报道过的材料Au25/ZIF-8和Au25@ZIF-8相比,实验证明 ZIF-8@Au25@ZIF-67可在温和条件下,高效的催化CO2的炔基化反应,并且该催化剂能够保持高活性的情况下多次循环使用。
本发明三明治纳米材料,其分子式为ZIF-8@Au25@ZIF-67,是以金属有机框架ZIF-8为内核,中间层为Au25纳米团簇,最外层为金属有机框架ZIF-67。所述三明治纳米材料中,Au25的负载量为1%,外层ZIF-67的厚度范围为2~25nm,优选为12nm。
本发明三明治纳米材料ZIF-8@Au25@ZIF-67的制备方法,包括如下步骤:
步骤1:按照常规方法分别合成ZIF-8(合成方法参见J.Membrane Sci.2017,540,155-164)、水溶性Au25纳米团簇(合成方法参见Angew.Chem.Int.Ed.2014,126,4711-471);
步骤2:将步骤1获得的Au25纳米团簇水溶液(2mg,10mL)滴加至ZIF-8的水相悬浊液(50mg,10mL)中,室温剧烈搅拌30分钟,离心分离,收集得到前驱体Au25/ZIF-8沉淀;
步骤3:将步骤2获得的前驱体Au25/ZIF-8均匀分散至10mL甲醇溶液中,得到Au25/ZIF-8 甲醇溶液;
步骤4:向步骤3获得的Au25/ZIF-8甲醇溶液中加入2-甲基咪唑和硝酸钴的甲醇溶液,室温下搅拌反应24小时,离心分离、洗涤并干燥,即可获得三明治纳米材料 ZIF-8@Au25@ZIF-67。
进一步地,步骤4中,调控外层ZIF-67厚度的硝酸钴和2-甲基咪唑的用量范围为:硝酸钴0.038~0.291g,2-甲基咪唑0.360~0.308g。
进一步地,步骤4中,向步骤3获得的Au25/ZIF-8甲醇溶液中先滴加硝酸钴的甲醇溶液,间隔半个小时之后,再滴加2-甲基咪唑的甲醇溶液,温和搅拌24小时,离心分离、洗涤并干燥,即可获得三明治纳米材料ZIF-8@Au25@ZIF-67,外层ZIF-67的厚度为2-25nm。
作为对比,Au25@ZIF-8纳米复合材料的合成方法参见Adv.Mater.2018,30,1704576。具体是将一定量的Au25和Zn(NO3)2溶于10mL去离子水中,超声分散30分钟,迅速将上述混合物倒入2-甲基咪唑的水溶液中(Zn(NO3)2与2-甲基咪唑的摩尔比为1:70),在剧烈搅拌下反应10分钟后,离心收集沉淀,洗涤并干燥,得到浅棕色粉末Au25@ZIF-8。其中Au25的负载量为1%。
本发明三明治纳米材料ZIF-8@Au25@ZIF-67的用途,是在末端炔羰基化的反应中作为催化剂使用。该三明治材料ZIF-8@Au25@ZIF-67作为催化剂对末端炔羧基化反应具有优异的活性和稳定性,从而有效实现了CO2的转化利用。
本发明三明治纳米材料ZIF-8@Au25@ZIF-67的应用,在末端炔羰基化的反应中作为催化剂,实现CO2的固载及转化。具体包括如下步骤:
向10mL的Schlenk反应瓶中依次加入0.5mmol末端炔、80mg ZIF-8@Au25@ZIF-67,0.24mmol Cs2CO3和1mL二甲亚砜,密封、抽真空,接二氧化碳气球,在50℃条件下搅拌反应12h,反应结束,去掉二氧化碳气球,待反应液温度冷却至室温,加入5mL蒸馏水,离心使固液分离;溶液中加1mmol Cs2CO3,然后用30mL二氯甲烷分三次萃取,水层用盐酸酸化 PH=1,再用40mL二氯甲烷分4次萃取,二氯甲烷层用饱和氯化钠洗涤,再用无水硫酸钠干燥,使用旋转蒸发仪除去溶剂得产物。
所述末端炔包括芳香族炔、N杂环炔、脂肪族炔等,具体选自苯乙炔、对甲基苯乙炔、对甲氧基苯乙炔、对硝基苯乙炔、对氟苯乙炔、2-吡啶乙炔、三甲基硅炔、环丙烷炔或炔丙胺等。
本发明的有益效果体现在:
1、材料合成制备简单,室温下即可进行反应。
2、采用化学配位法原理制备材料,材料性能稳定,适用范围较广。
3、与文献报道过的材料Au25/ZIF-8和Au25@ZIF-8相比,本发明三明治纳米材料ZIF-8@Au25@ZIF-67作为催化剂能够在温和条件下催化末端炔的羰基化反应,并且具有优异的催化活性和稳定性。
附图说明
图1是Au25纳米团簇的紫外可见光谱。通过图1可以看出其吸收峰在440,546,670,780nm。
图2是Au25/ZIF-8的TEM图,通过图2可以看出Au25/ZIF-8为正十二面体结构,颗粒大小不变,负载均匀。
图3是ZIF-8@Au25@ZIF-67的TEM图,通过图3可以看出ZIF-8@Au25@ZIF-67为三层夹心正十二面体结构,颗粒大小不变,负载均匀。
图4是不同催化剂的催化反应活性。从图4中可以看出,产率分别为 99.0%(ZIF-8@Au25@ZIF-67),40.5%(Au25/ZIF-8),38.0%(Au25@ZIF-8),11.0%(Au25),27.9% (ZIF-8)和52.0%(ZIF-8@ZIF-67)。由此可知,在不同催化剂中,ZIF-8@Au25@ZIF-67的催化活性最高。
图5是ZIF-8@Au25@ZIF-67的循环性能测试。从图5中可以看出,该催化剂循环5次之后稳定性依然保持良好。
具体实施方式
下面通过具体的实施例对本发明技术方案作进一步分析说明。
实施例1:Au25纳米团簇的制备
12毫克L-半胱氨酸溶于10毫升去离子水中置于50毫升反应瓶中,加入100微升,0.2g/mL 的HAuCl4水溶液。接着加入0.3mL,1M的氢氧化钠水溶液。最后取100微升配置溶液A(将 21mg硼氢化钠与5mL,0.2M的氢氧化钠水溶液混合)。反应6小时,整个过程都在匀速搅拌情况下完成。反应结束后产物用10,000转,离心5分钟收集溶液部分,将溶液中加入2倍量的乙腈溶液,离心收集沉淀,再次用乙腈洗涤沉淀3次,得到较为纯净的Au25纳米团簇。图1为Au25纳米团簇的紫外可见光谱。通过图1可以看出其吸收峰在440,546,670,780nm。
实施例2:ZIF-8的制备
6.8mmol的2-甲基咪唑溶于20mL去离子水,然后2mmol的Zn(NO3)2·6H2O溶于20mL的DMF。搅拌情况下向咪唑溶液快速注入Zn溶液,室温快速搅拌1.5小时。反应结束后,产物用10,000转的转速离心8分钟,然后用甲醇清洗沉淀5次,每次转速3分钟,最后60℃真空烘箱中烘干得到ZIF-8。
实施例3:Au25@ZIF-8的制备
将2mg Au25和Zn(NO3)2溶于10mL去离子水中,超声分散30分钟,迅速将上述混合物倒入 2-甲基咪唑的水溶液中(Zn(NO3)2与2-甲基咪唑的摩尔比为1:70),在剧烈搅拌下反应10分钟后,将产生的沉淀物通过离心机10,000转3分钟离心收集沉淀,沉淀分别用10mL去离子水和10mL 甲醇各洗涤两次,然后将沉淀置于真空干燥箱中50℃,得到浅棕色粉末Au25@ZIF-8。
实施例4:Au25/ZIF-8的制备,具体步骤如下:
将2mg Au25溶于10毫升去离子水中,然后滴加10毫升ZIF-8(100毫克)的水溶液,剧烈搅拌 30分钟;随后,混合溶液通过离心机10,000转2分钟离心收集得到Au25/ZIF-8,得到的产物在 100℃真空烘箱烘干。图2为Au25/ZIF-8的TEM图,通过图2可以看出Au25均匀负载在ZIF-8上,颗粒大小不变,负载均匀。
实施例5:ZIF-8@Au25@ZIF-67的制备
将50mg Au25/ZIF-8分散于10mL甲醇中,置于50mL反应瓶中,然后缓慢搅拌,将10mL含 0.146g Cn(NO3)2·6H2O的甲醇溶液滴入反应瓶中,30分钟后将10mL含0.154g 2-甲基咪唑的甲醇溶液加入混合溶液中,混合溶液在室温下搅拌24小时后,用离心机离心收集沉淀,用30mL 甲醇洗涤五次,产物在真空烤箱中50℃干燥,所得到的复合材料即为ZIF-8@Au25@ZIF-67(外层厚度为12nm)。图3是ZIF-8@Au25@ZIF-67的TEM图,通过图3可以看出ZIF-8@Au25@ZIF-67 为三层夹心结构,颗粒大小不变,负载均匀。
实施例6:外层厚度为2nm的ZIF-8@Au25@ZIF-67催化苯乙炔羰基化合成苯丙炔酸。
向10mL的Schlenk反应瓶中依次加入苯乙炔、80mg外层厚度为2nm的 ZIF-8@Au25@ZIF-67,0.24mmol Cs2CO3和1mL二甲亚砜,密封、抽真空、接二氧化碳气球,在50℃条件下搅拌反应12h,反应结束,去掉二氧化碳气球,待反应液温度冷却至室温,加入5mL蒸馏水,离心使固液分离;溶液中加1mmol Cs2CO3,然后用30mL二氯甲烷分三次萃取,水层用盐酸酸化PH=1,再用40mL二氯甲烷分4次萃取,二氯甲烷层用饱和氯化钠洗涤,再用无水硫酸钠干燥,使用旋转蒸发仪除去溶剂得产物,产率为65.0%。
实施例7:外层厚度为12nm的ZIF-8@Au25@ZIF-67催化苯乙炔羰基化合成苯丙炔酸。
向10mL的Schlenk反应瓶中依次加入苯乙炔、80mg外层厚度为12nm的 ZIF-8@Au25@ZIF-67,0.24mmol Cs2CO3和1mL二甲亚砜,密封、抽真空、接二氧化碳气球,在50℃条件下搅拌反应12h,反应结束,去掉二氧化碳气球,待反应液温度冷却至室温,加入5mL蒸馏水,离心使固液分离;溶液中加1mmol Cs2CO3,然后用30mL二氯甲烷分三次萃取,水层用盐酸酸化PH=1,再用40mL二氯甲烷分4次萃取,二氯甲烷层用饱和氯化钠洗涤,再用无水硫酸钠干燥,使用旋转蒸发仪除去溶剂得产物,产率为99.0%。
实施例8:外层厚度为25nm的ZIF-8@Au25@ZIF-67催化苯乙炔羰基化合成苯丙炔酸。
向10mL的Schlenk反应瓶中依次加入苯乙炔、80mg外层厚度为25nm的 ZIF-8@Au25@ZIF-67,0.24mmol Cs2CO3和1mL二甲亚砜,密封、抽真空、接二氧化碳气球,在50℃条件下搅拌反应12h,反应结束,去掉二氧化碳气球,待反应液温度冷却至室温,加入5mL蒸馏水,离心使固液分离;溶液中加1mmol Cs2CO3,然后用30mL二氯甲烷分三次萃取,水层用盐酸酸化PH=1,再用40mL二氯甲烷分4次萃取,二氯甲烷层用饱和氯化钠洗涤,再用无水硫酸钠干燥,使用旋转蒸发仪除去溶剂得产物,产率为70.0%。
实施例9:不同催化剂催化苯乙炔羰基化合成苯丙炔酸。
向10mL的Schlenk反应瓶中依次加入苯乙炔、80mg不同催化剂(分别为Au25,ZIF-8,Au25/ZIF-8,ZIF-8@ZIF-67,ZIF-8@Au25@ZIF-67(外层厚度为12nm)),0.24mmol Cs2CO3和1mL二甲亚砜,密封、抽真空、接二氧化碳气球,在50℃条件下搅拌反应12h,反应结束,去掉二氧化碳气球,待反应液温度冷却至室温,加入5mL蒸馏水,离心使固液分离;溶液中加1mmolCs2CO3,然后用30mL二氯甲烷分三次萃取,水层用盐酸酸化PH=1,再用40mL 二氯甲烷分4次萃取,二氯甲烷层用饱和氯化钠洗涤,再用无水硫酸钠干燥,使用旋转蒸发仪除去溶剂得产物,产率如图4所示。从图4中可以看出,产率分别为 99.0%(ZIF-8@Au25@ZIF-67),40.5%(Au25/ZIF-8),38.0%(Au25@ZIF-8),11.0%(Au25),27.9% (ZIF-8)和52.0%(ZIF-8@ZIF-67)。由此可知,在不同催化剂中,外层厚度为12nm的 ZIF-8@Au25@ZIF-67的催化活性最高。
实施例10:外层厚度为12nm的ZIF-8@Au25@ZIF-67催化4-硝基苯乙炔羰基化合成4-硝基苯丙炔酸。
向10mL的Schlenk反应瓶中依次加入4-氯苯乙炔、80mg ZIF-8@Au25@ZIF-67催化剂, 0.24mmol Cs2CO3和1mL二甲亚砜,密封、抽真空、接二氧化碳气球,在50℃条件下搅拌反应12h,反应结束,去掉二氧化碳气球;待反应液温度冷却至室温,加入5mL蒸馏水,离心使固液分离;溶液中加1mmol Cs2CO3,然后用30mL二氯甲烷分三次萃取,水层用盐酸酸化 PH=1,再用40mL二氯甲烷分4次萃取,二氯甲烷层用饱和氯化钠洗涤,再用无水硫酸钠干燥,使用旋转蒸发仪除去溶剂得产物,产率为84.5%。
实施例11:外层厚度为12nm的ZIF-8@Au25@ZIF-67催化4-氟苯乙炔羰基化合成4-氟苯丙炔酸。
向10mL的Schlenk反应瓶中依次加入4-硝基苯乙炔、80mgZIF-8@Au25@ZIF-67催化剂, 0.24mmol Cs2CO3和1mL二甲亚砜,密封、抽真空、接二氧化碳气球,在50℃条件下搅拌反应12h,反应结束,去掉二氧化碳气球,待反应液温度冷却至室温,加入5mL蒸馏水,离心使固液分离;溶液中加1mmol Cs2CO3,然后用30mL二氯甲烷分三次萃取,水层用盐酸酸化 PH=1,再用40mL二氯甲烷分4次萃取,二氯甲烷层用饱和氯化钠洗涤,再用无水硫酸钠干燥,使用旋转蒸发仪除去溶剂得产物,产率为83.1%。
实施例12:外层厚度为12nm的ZIF-8@Au25@ZIF-67催化4-甲基苯乙炔羰基化合成4-甲基苯丙炔酸。
向10mL的Schlenk反应瓶中依次加入4-甲基苯乙炔、80mg ZIF-8@Au25@ZIF-6催化剂, 0.24mmol Cs2CO3和1mL二甲亚砜,密封、抽真空、接二氧化碳气球,在50℃条件下搅拌反应12h,反应结束,去掉二氧化碳气球,待反应液温度冷却至室温,加入5mL蒸馏水,离心使固液分离;溶液中加1mmol Cs2CO3,然后用30mL二氯甲烷分三次萃取,水层用盐酸酸化 PH=1,再用40mL二氯甲烷分4次萃取,二氯甲烷层用饱和氯化钠洗涤,再用无水硫酸钠干燥,使用旋转蒸发仪除去溶剂得产物,产率为85.3%。
实施例13:外层厚度为12nm的ZIF-8@Au25@ZIF-67催化4-甲氧基苯乙炔羰基化合成4-甲氧基苯丙炔酸。
向10mL的Schlenk反应瓶中依次加入4-甲氧基苯乙炔、80mg ZIF-8@Au25@ZIF-67催化剂,0.24mmol Cs2CO3和1mL二甲亚砜,密封、抽真空、接二氧化碳气球,在50℃条件下搅拌反应12h,反应结束,去掉二氧化碳气球,待反应液温度冷却至室温,加入5mL蒸馏水,离心使固液分离;溶液中加1mmol Cs2CO3,然后用30mL二氯甲烷分三次萃取,水层用盐酸酸化PH=1,再用40mL二氯甲烷分4次萃取,二氯甲烷层用饱和氯化钠洗涤,再用无水硫酸钠干燥,使用旋转蒸发仪除去溶剂得产物,产率为87.9%。
实施例14:外层厚度为12nm的ZIF-8@Au25@ZIF-67催化2-吡啶乙炔羰基化合成3-(2-吡啶基)丙炔酸。
向10mL的Schlenk反应瓶中依次加入2-吡啶乙炔、80mg ZIF-8@Au25@ZIF-67催化剂, 0.24mmol Cs2CO3和1mL二甲亚砜,密封、抽真空、接二氧化碳气球,在50℃条件下搅拌反应12h,反应结束,去掉二氧化碳气球,待反应液温度冷却至室温,加入5mL蒸馏水,离心使固液分离;溶液中加1mmol Cs2CO3,然后用30mL二氯甲烷分三次萃取,水层用盐酸酸化 PH=1,再用40mL二氯甲烷分4次萃取,二氯甲烷层用饱和氯化钠洗涤,再用无水硫酸钠干燥,使用旋转蒸发仪除去溶剂得产物,产率为89.4%。
实施例15:外层厚度为12nm的ZIF-8@Au25@ZIF-67催化环丙炔羰基化合成环丙炔酸。
向10mL的Schlenk反应瓶中依次加入环丙炔、80mg ZIF-8@Au25@ZIF-67催化剂,0.24mmol Cs2CO3和1mL二甲亚砜,密封、抽真空、接二氧化碳气球,在50℃条件下搅拌反应12h,反应结束,去掉二氧化碳气球。待反应液温度冷却至室温,加入5mL蒸馏水,离心使固液分离;溶液中加1mmol Cs2CO3,然后用30mL二氯甲烷分三次萃取,水层用盐酸酸化 PH=1,再用40mL二氯甲烷分4次萃取,二氯甲烷层用饱和氯化钠洗涤,再用无水硫酸钠干燥,使用旋转蒸发仪除去溶剂得产物,产率为84.4%。
实施例16:外层厚度为12nm的ZIF-8@Au25@ZIF-67催化炔丙胺羰基化合成炔丙胺酸。
向10mL的Schlenk反应瓶中依次加入2-氨基乙炔、80mg ZIF-8@Au25@ZIF-67催化剂, 0.24mmol Cs2CO3和1mL二甲亚砜,密封、抽真空、接二氧化碳气球,在50℃条件下搅拌反应12h,反应结束,去掉二氧化碳气球,待反应液温度冷却至室温,加入5mL蒸馏水,离心使固液分离;溶液中加1mmol Cs2CO3,然后用30mL二氯甲烷分三次萃取,水层用盐酸酸化 PH=1,再用40mL二氯甲烷分4次萃取,二氯甲烷层用饱和氯化钠洗涤,再用无水硫酸钠干燥,使用旋转蒸发仪除去溶剂得产物,产率为82.9%。
实施例17:外层厚度为12nm的ZIF-8@Au25@ZIF-67催化三甲基硅炔羰基化合成3-(三甲基硅基)丙炔酸。
向10mL的Schlenk反应瓶中依次加入2-氨基乙炔、80mg ZIF-8@Au25@ZIF-67催化剂,0.24mmol Cs2CO3和1mL二甲亚砜,密封、抽真空、接二氧化碳气球,在50℃条件下搅拌反应12h,反应结束,去掉二氧化碳气球,待反应液温度冷却至室温,加入5mL蒸馏水,离心使固液分离;溶液中加1mmol Cs2CO3,然后用30mL二氯甲烷分三次萃取,水层用盐酸酸化 PH=1,再用40mL二氯甲烷分4次萃取,二氯甲烷层用饱和氯化钠洗涤,再用无水硫酸钠干燥,使用旋转蒸发仪除去溶剂得产物,产率为88.8%。
实施例18:外层厚度为12nm的ZIF-8@Au25@ZIF-67催化苯乙炔羰基化合成苯丙炔酸的循环性能测试
向10mL的Schlenk反应瓶中依次加入苯乙炔、80mg循环后的ZIF-8@Au25@ZIF-67催化剂,0.24mmol Cs2CO3和1mL二甲亚砜,密封、抽真空、接二氧化碳气球,在50℃条件下搅拌反应12h,反应结束,去掉二氧化碳气球,待反应液温度冷却至室温,加入5mL蒸馏水,离心使固液分离;溶液中加1mmol Cs2CO3,然后用30mL二氯甲烷分三次萃取,水层用盐酸酸化PH=1,再用40mL二氯甲烷分4次萃取,二氯甲烷层用饱和氯化钠洗涤,再用无水硫酸钠干燥,使用旋转蒸发仪除去溶剂得产物。得到的目标产物的产率与循环次数关系如图5所示,表明该催化剂循环5次之后稳定性依然保持良好。
Claims (7)
1.一种三明治纳米材料ZIF-8@Au25@ZIF-67的应用,其特征在于:在末端炔羰基化的反应中作为催化剂,实现CO2的固载及转化;
所述三明治纳米材料的分子式为ZIF-8@Au25@ZIF-67,是以金属有机框架ZIF-8为内核,中间层为Au25纳米团簇,最外层为金属有机框架ZIF-67;
所述三明治纳米材料中,Au25的负载量为1%,外层ZIF-67的厚度范围为2~25 nm。
2.根据权利要求1所述的应用,其特征在于:
外层ZIF-67的厚度为12nm。
3.根据权利要求1所述的应用,其特征在于包括如下步骤:
向10mL的Schlenk反应瓶中依次加入0.5mmol末端炔、80mg ZIF-8@Au25@ZIF-67,0.24mmol Cs2CO3和1mL二甲亚砜,密封、抽真空,接二氧化碳气球,在50℃条件下搅拌反应12h,反应结束,去掉二氧化碳气球,待反应液温度冷却至室温,加入5mL蒸馏水,离心使固液分离;溶液中加1mmol Cs2CO3,然后用二氯甲烷萃取,水层用盐酸酸化PH=1,再用二氯甲烷萃取,二氯甲烷层用饱和氯化钠洗涤,再用无水硫酸钠干燥,使用旋转蒸发仪除去溶剂得产物。
4.根据权利要求3所述的应用,其特征在于:
所述末端炔包括芳香族炔、N杂环炔、脂肪族炔。
5.根据权利要求1所述的应用,其特征在于所述三明治纳米材料ZIF-8@Au25@ZIF-67的制备方法包括如下步骤:
步骤1:按照常规方法分别合成ZIF-8以及水溶性Au25纳米团簇;
步骤2:将含有2mgAu25纳米团簇的水溶液10mL滴加至10mL含有50mgZIF-8的水相悬浊液中,室温剧烈搅拌30分钟,离心分离,收集得到前驱体Au25/ZIF-8沉淀;
步骤3:将步骤2获得的前驱体Au25/ZIF-8均匀分散至10mL甲醇溶液中,得到Au25/ZIF-8甲醇溶液;
步骤4:向步骤3获得的Au25/ZIF-8甲醇溶液中加入2-甲基咪唑和硝酸钴的甲醇溶液,室温下搅拌反应24小时,离心分离、洗涤并干燥,即可获得三明治纳米材料ZIF-8@Au25@ZIF-67。
6.根据权利要求5所述的应用,其特征在于:
步骤4中,调控外层ZIF-67厚度的硝酸钴和2-甲基咪唑的用量范围为:硝酸钴0.038~0.291g,2-甲基咪唑0.360~0.308g。
7.根据权利要求5或6所述的应用,其特征在于:
步骤4中,向步骤3获得的Au25/ZIF-8甲醇溶液中先滴加硝酸钴的甲醇溶液,间隔半个小时之后,再滴加2-甲基咪唑的甲醇溶液,温和搅拌24小时,离心分离、洗涤并干燥,即可获得三明治纳米材料ZIF-8@Au25@ZIF-67,外层ZIF-67的厚度为2-25nm。
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