CN110433867A - 一种手性Cu/Zn-MOF/NiF纳米复合催化剂的制备方法和应用 - Google Patents
一种手性Cu/Zn-MOF/NiF纳米复合催化剂的制备方法和应用 Download PDFInfo
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- 239000013094 zinc-based metal-organic framework Substances 0.000 title claims abstract description 56
- 239000013084 copper-based metal-organic framework Substances 0.000 title claims abstract description 53
- 239000003054 catalyst Substances 0.000 title claims abstract description 41
- 239000002114 nanocomposite Substances 0.000 title claims abstract description 38
- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 claims abstract description 24
- 239000003446 ligand Substances 0.000 claims abstract description 23
- 239000000463 material Substances 0.000 claims abstract description 18
- 230000004913 activation Effects 0.000 claims abstract description 15
- 239000003792 electrolyte Substances 0.000 claims abstract description 15
- UMRSVAKGZBVPKD-UHFFFAOYSA-N acetic acid;copper Chemical compound [Cu].CC(O)=O UMRSVAKGZBVPKD-UHFFFAOYSA-N 0.000 claims abstract description 12
- 238000005516 engineering process Methods 0.000 claims abstract description 12
- 238000004070 electrodeposition Methods 0.000 claims abstract description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 29
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 28
- 229910052759 nickel Inorganic materials 0.000 claims description 14
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 14
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 10
- 229920002338 polyhydroxyethylmethacrylate Polymers 0.000 claims description 10
- 235000008001 rakum palm Nutrition 0.000 claims description 10
- 239000010949 copper Substances 0.000 claims description 8
- 239000011701 zinc Substances 0.000 claims description 8
- 238000000151 deposition Methods 0.000 claims description 7
- 229910052697 platinum Inorganic materials 0.000 claims description 7
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
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- 230000008021 deposition Effects 0.000 claims description 5
- ZOMNIUBKTOKEHS-UHFFFAOYSA-L dimercury dichloride Chemical compound Cl[Hg][Hg]Cl ZOMNIUBKTOKEHS-UHFFFAOYSA-L 0.000 claims description 5
- 238000002604 ultrasonography Methods 0.000 claims description 5
- 238000005406 washing Methods 0.000 claims description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 3
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- UQFSVBXCNGCBBW-UHFFFAOYSA-M tetraethylammonium iodide Chemical compound [I-].CC[N+](CC)(CC)CC UQFSVBXCNGCBBW-UHFFFAOYSA-M 0.000 description 2
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Abstract
本发明公开了一种手性Cu/Zn‑MOF/NiF纳米复合催化剂的制备方法以及基于该催化剂用于苯乙酮不对称电还原的应用,属于电合成技术、纳米材料技术领域。其主要步骤是将醋酸铜溶液、硝酸锌溶液和配体溶液混合,制得电解液;在三电极体系中,采用恒电位电沉积工艺,将得到的的材料,置于微波炉中250 W活化后,得到手性Cu/Zn‑MOF/NiF纳米复合催化剂;将该催化剂苯乙酮不对称电还原的应用,工艺简单,反应能耗低,具有良好的工业前景。
Description
技术领域
本发明公开了一种手性Cu/Zn-MOF/NiF纳米复合催化剂的制备方法以及用于苯乙酮不对称电还原的应用,属于电合成技术、纳米材料技术领域。
背景技术
手性现象在自然界中普遍存在。不同立体构型的对映异构体往往表现出不同甚至相反的性能。获得光学异构体纯手性化合物在生物学、化学、药学、农业或非线性光学材料行业都非常重要。寻找高选择性的手性化合物的有效合成方法一直是现代化学工作者的巨大挑战。不对称催化合成方法是获得对映异构体纯手性化合物中最具有经济效益的合成方法,同时也具有挑战性。
电化学合成技术反应条件温和、安全。电化学反应中只需要简单控制电极电势和催化剂,即可调整高能量的中间体和手性对映体产物的比例。因此。电化学方法是一种有效的合成方法和技术,应用电化学技术进行不对称合成,获得光学纯的手性化合物具有重大意义。
寻找高效的不对称催化剂是不对称催化领域的关键步骤。不对称催化剂主要有三类,金属配合物催化剂、生物催化剂和有机催化剂。手性MOF作为一种新型金属配合物催化剂引起全球科研者的广泛关注。手性MOF是将金属离子和手性有机配体通过自组装的方式形成的金属-有机框架物,MOF材料超大的比表面积与孔隙率、特殊的孔道结构、开放的金属位点,使其拥有巨大的吸附能力和装载能力;同时,MOF材料结构可设计、可调控, 结构变化灵活等优点。
发明内容
本发明的技术任务之一是为了弥补现有技术的不足,提供一种手性Cu/Zn-MOF/NiF纳米复合催化剂的制备方法,该方法所用原料成本低,制备工艺简单,反应能耗低,具有工业应用前景。
本发明的技术任务之二是提供所述催化剂的用途,即将该催化剂用于苯乙酮不对称电还原的应用,具有良好的电催化活性与稳定性。
为实现上述目的,本发明采用的技术方案如下:
1.一种手性Cu/Zn-MOF/NiF纳米复合催化剂的制备方法
将0.8-1.0 mmol的Cu(CH3COO)2·H2O与8-10 mL水共混,得到醋酸铜溶液;
将0.8-1.0 mmol的Zn(NO3)2·6H2O溶于8-10 mL水中,得到澄清的硝酸锌溶液;
将0.8-1.0 mmol 配体H2sala和0.8-1.0 mmol LiOH加入到8-10 mL水中,搅拌25-30min,得到澄清的配体溶液;
将醋酸铜溶液、硝酸锌溶液、配体溶液室温混合均匀作为电解液,在三电极体系中,1.0cm × 1.0 cm的活化镍网NiF为工作电极、铂片为辅助电极、甘汞电极为参比电极,采用恒电位电沉积工艺,在-1.0~ -1.5 V的沉积电压下沉积10-15 min制得手性Cu/Zn-MOF/NiF纳米复合材料;水洗后,置于微波炉中250 W活化3 min,制得活化手性Cu/Zn-MOF/NiF纳米复合材料,即手性Cu/Zn-MOF/NiF纳米复合催化剂;
所述活化镍网NiF,是将1.0 cm × 1.0 cm的镍网NiF在质量分数为1.5%的稀盐酸中180 W超声2 min去除表面杂物,然后分别用蒸馏水、乙醇清洗后制得。
所述sala,构造式如下:
。
所述Cu/Zn-MOF,为两种金属有机框架物Cu-MOF和Zn-MOF的共掺杂复合才材料;
所述Cu/Zn-MOF/NiF纳米复合催化剂,是Cu-MOF和Zn-MOF共掺杂的纳米晶体负载在镍网NiF上具有纳米-微米多孔的三维复合材料;
Cu-MOF的基本结构单元为[{Cu(sala)(H2O)}2]·2H2O,是由一个Cu2+,一个配体sala2-,2个主体水分子和2个客体水分子构成;Zn-MOF的基本结构单元为[{Zn(sala)(H2O)}2]·2H2O,是由一个Zn2+,一个配体sala2-,2个主体水分子和2个客体水分子构成。
2.如上所述的制备方法制备的手性Cu/Zn-MOF/NiF纳米复合催化剂用于苯乙酮不对称电还原的应用,步骤如下:
(1)电解液的配制
将0.1-0.3 M 季铵盐和0.1-0.3 M 苯乙酮依次缓慢加入8-12 mL 的溶剂MeCN-H2O中,180 W超声3 min,得到澄清的电解液;所述溶剂MeCN-H2O,MeCN和H2O的体积比为7:3-9:1;
所述季铵盐选自四乙基溴化铵、四乙基碘化铵或四乙基氯化铵;
(2)苯乙酮的不对称电还原
采用恒电位电解工艺,在三电极体系中,用手性Cu/Zn-MOF/NiF纳米复合催化剂作为工作电极,Ag/AgCl作为参比电极,铂片作为辅助电极,使用步骤(1)制得的电解液,在-0.8~-1.5 V的电压下电还原2-3 h,将电解液用20 mL无水乙醚分别萃取3次、无水硫酸镁干燥1-2h后得到R-(+)-1-苯基乙醇和S-(+)-1-苯基乙醇的混合物,通过手性高相液相色谱进行定量检测,R-(+)-1-苯基乙醇和S-(+)-1-苯基乙醇ee值为21.6%-25.1%。
本发明有益的技术效果如下:
(1)本发明手性Cu/Zn-MOF/NiF纳米复合催化剂,是将醋酸铜溶液、硝酸锌溶液和配体溶液混合制得的电解液,在三电极体系中,采用恒电位电沉积工艺制得,继续微波炉中250W活化后制得,该制备工艺简单,反应能耗低,具有良好的工业前景。
(2)本发明手性Cu/Zn-MOF/NiF纳米复合材料置于微波炉中250 W活化,暴露了更多的活性位点,且电沉积制备的具有纳米-微米多孔状混合MOF纳米晶阵列显著增大了比表面积;Zn-MOF和Cu-MOF的掺杂使得手性Cu/Zn-MOF/NiF纳米复合催化剂,发挥了两者的协同作用,提高了该催化剂的催化活性。
具体实施方式
下面结合实施例对本发明作进一步描述,但本发明的保护范围不仅局限于实施例,该领域专业人员对本发明技术方案所作的改变,均应属于本发明的保护范围内。
实施例1一种手性Cu/Zn-MOF/NiF纳米复合催化剂的制备方法
将0.8 mmol的Cu(CH3COO)2·H2O与8-10 mL水共混,得到醋酸铜溶液;
将0.8 mmol的Zn(NO3)2·6H2O溶于8-10 mL水中,得到澄清的硝酸锌溶液;
将0.8 mmol 配体H2sala和0.8-1.0 mmol LiOH加入到8-10 mL水中,搅拌25-30 min,得到澄清的配体溶液;
将醋酸铜溶液、硝酸锌溶液、配体溶液室温混合均匀作为电解液,在三电极体系中,1.0cm × 1.0 cm的活化镍网NiF为工作电极、铂片为辅助电极、甘汞电极为参比电极,采用恒电位电沉积工艺,在-1.0 V的沉积电压下沉积15 min制得手性Cu/Zn-MOF/NiF纳米复合材料;水洗后,置于微波炉中250 W活化3 min,制得活化手性Cu/Zn-MOF/NiF纳米复合材料,即手性Cu/Zn-MOF/NiF纳米复合催化剂。
实施例2 一种手性Cu/Zn-MOF/NiF纳米复合催化剂的制备方法
将0.9 mmol的Cu(CH3COO)2·H2O与9 mL水共混,得到醋酸铜溶液;
将0.9 mmol的Zn(NO3)2·6H2O溶于9 mL水中,得到澄清的硝酸锌溶液;
将0.9 mmol 配体H2sala和0.9 mmol LiOH加入到9 mL水中,搅拌27 min,得到澄清的配体溶液;
将醋酸铜溶液、硝酸锌溶液、配体溶液室温混合均匀作为电解液,在三电极体系中,1.0cm × 1.0 cm的活化镍网NiF为工作电极、铂片为辅助电极、甘汞电极为参比电极,采用恒电位电沉积工艺,在-1.3 V的沉积电压下沉积15 min制得手性Cu/Zn-MOF/NiF纳米复合材料;水洗后,置于微波炉中250 W活化3 min,制得活化手性Cu/Zn-MOF/NiF纳米复合材料,即手性Cu/Zn-MOF/NiF纳米复合催化剂。
实施例3 一种手性Cu/Zn-MOF/NiF纳米复合催化剂的制备方法
将1.0 mmol的Cu(CH3COO)2·H2O与10 mL水共混,得到醋酸铜溶液;
将1.0 mmol的Zn(NO3)2·6H2O溶于10 mL水中,得到澄清的硝酸锌溶液;
将1.0 mmol 配体H2sala和1.0 mmol LiOH加入到10 mL水中,搅拌30 min,得到澄清的配体溶液;
将醋酸铜溶液、硝酸锌溶液、配体溶液室温混合均匀作为电解液,在三电极体系中,1.0cm × 1.0 cm的活化镍网NiF为工作电极、铂片为辅助电极、甘汞电极为参比电极,采用恒电位电沉积工艺,在-1.5 V的沉积电压下沉积10 min制得手性Cu/Zn-MOF/NiF纳米复合材料;水洗后,置于微波炉中250 W活化3 min,制得活化手性Cu/Zn-MOF/NiF纳米复合材料,即手性Cu/Zn-MOF/NiF纳米复合催化剂。
实施例4 活化镍网NiF的方法
实施例1、实施例2或实施例3所述活化镍网NiF,是将1.0 cm × 1.0 cm的镍网NiF在质量分数为1.5%的稀盐酸中180 W超声2 min去除表面杂物,然后分别用蒸馏水、乙醇清洗后制得。
实施例5 sala的结构
实施例1、实施例2或实施例3所述sala,构造式如下:
。
实施例6 Cu/Zn-MOF/NiF纳米复合催化剂的结构
实施例1、实施例2或实施例3所述Cu/Zn-MOF,为两种金属有机框架物Cu-MOF和Zn-MOF的共掺杂复合才材料;所述Cu/Zn-MOF/NiF纳米复合催化剂,是Cu-MOF和Zn-MOF共掺杂的纳米晶体负载在镍网NiF上具有纳米-微米多孔的三维复合材料;Cu-MOF的基本结构单元为[{Cu(sala)(H2O)}2]·2H2O,是由一个Cu2+,一个配体sala2-,2个主体水分子和2个客体水分子构成;Zn-MOF的基本结构单元为[{Zn(sala)(H2O)}2]·2H2O,是由一个Zn2+,一个配体sala2-,2个主体水分子和2个客体水分子构成。
实施例7 一种手性Cu/Zn-MOF/NiF纳米复合催化剂用于苯乙酮不对称电还原的应用
(1)电解液的配制
将0.1-0.3 M 季铵盐和0.1-0.3 M 苯乙酮依次缓慢加入8-12 mL 的溶剂MeCN-H2O中,180 W超声3 min,得到澄清的电解液;所述溶剂MeCN-H2O,MeCN和H2O的体积比为7:3-9:1;
所述季铵盐选自四乙基溴化铵、四乙基碘化铵或四乙基氯化铵;
(2)苯乙酮的不对称电还原
采用恒电位电解工艺,在三电极体系中,用手性Cu/Zn-MOF/NiF纳米复合催化剂作为工作电极,Ag/AgCl作为参比电极,铂片作为辅助电极,使用步骤(1)制得的电解液,在-0.8~-1.5 V的电压下电还原2-3 h,将电解液用20 mL无水乙醚分别萃取3次、无水硫酸镁干燥1-2h后得到R-(+)-1-苯基乙醇和S-(+)-1-苯基乙醇的混合物,通过手性高效液相色谱进行定量检测;
所述手性Cu/Zn-MOF/NiF纳米复合催化剂,选自实施例1、实施例2或实施例3;
实施例1制得手性Cu/Zn-MOF/NiF纳米复合催化剂, 合成R-(+)-1-苯基乙醇和S-(+)-1-苯基乙醇的ee值为21.6%;实施例2制得手性Cu/Zn-MOF/NiF纳米复合催化剂,合成R-(+)-1-苯基乙醇和S-(+)-1-苯基乙醇的ee值为25.1%;实施例3制得手性Cu/Zn-MOF/NiF纳米复合催化剂,合成R-(+)-1-苯基乙醇和S-(+)-1-苯基乙醇的ee值为23.4%。
Claims (5)
1.一种手性Cu/Zn-MOF/NiF纳米复合催化剂的制备方法,其特征在于,步骤如下:
将0.8-1.0 mmol的Cu(CH3COO)2·H2O与8-10 mL水共混,得到醋酸铜溶液;
将0.8-1.0 mmol的Zn(NO3)2·6H2O溶于8-10 mL水中,得到澄清的硝酸锌溶液;
将0.8-1.0 mmol 配体H2sala和0.8-1.0 mmol LiOH加入到8-10 mL水中,搅拌25-30min,得到澄清的配体溶液;
将醋酸铜溶液、硝酸锌溶液、配体溶液室温混合均匀作为电解液,在三电极体系中,1.0cm × 1.0 cm的活化镍网NiF为工作电极、铂片为辅助电极、甘汞电极为参比电极,采用恒电位电沉积工艺,在-1.0~ -1.5 V的沉积电压下沉积10-15 min制得手性Cu/Zn-MOF/NiF纳米复合材料;水洗后,置于微波炉中250 W活化3 min,制得活化手性Cu/Zn-MOF/NiF纳米复合材料,即手性Cu/Zn-MOF/NiF纳米复合催化剂。
2.根据权利要求1所述的一种手性Cu/Zn-MOF/NiF纳米复合催化剂的制备方法,其特征在于,所述活化镍网NiF,是将1.0 cm × 1.0 cm的镍网NiF在质量分数为1.5%的稀盐酸中180 W超声2 min去除表面杂物,然后分别用蒸馏水、乙醇清洗后制得。
3.根据权利要求1所述的一种手性Cu/Zn-MOF/NiF纳米复合催化剂的制备方法,其特征在于,所述sala,构造式如下:
。
4.根据权利要求1所述的一种手性Cu/Zn-MOF/NiF纳米复合催化剂的制备方法,其特征在于,所述Cu/Zn-MOF,为两种金属有机框架物Cu-MOF和Zn-MOF的共掺杂复合材料,Cu-MOF的基本结构单元为[{Cu(sala)(H2O)}2]·2H2O,是由一个Cu2+,一个配体sala2-,2个主体水分子和2个客体水分子构成;Zn-MOF的基本结构单元为[{Zn(sala)(H2O)}2]·2H2O,是由一个Zn2+,一个配体sala2-,2个主体水分子和2个客体水分子构成。
5.根据权利要求1所述的制备方法制备的手性Cu/Zn-MOF/NiF纳米复合催化剂用于苯乙酮不对称电还原的应用。
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