CN113457743A - 一种纳米铬酸铋/g-C3N4改性MOFs复合材料制备方法及其应用 - Google Patents
一种纳米铬酸铋/g-C3N4改性MOFs复合材料制备方法及其应用 Download PDFInfo
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- 239000012621 metal-organic framework Substances 0.000 title claims abstract description 77
- 239000002131 composite material Substances 0.000 title claims abstract description 56
- DHMGMTYGCBZFST-UHFFFAOYSA-N dibismuth;dioxido(dioxo)chromium Chemical compound [Bi+3].[Bi+3].[O-][Cr]([O-])(=O)=O.[O-][Cr]([O-])(=O)=O.[O-][Cr]([O-])(=O)=O DHMGMTYGCBZFST-UHFFFAOYSA-N 0.000 title claims abstract description 55
- 238000000034 method Methods 0.000 title description 7
- 238000003756 stirring Methods 0.000 claims abstract description 35
- 238000002360 preparation method Methods 0.000 claims abstract description 26
- -1 imidazole ester Chemical class 0.000 claims abstract description 25
- 239000003446 ligand Substances 0.000 claims abstract description 24
- 239000013110 organic ligand Substances 0.000 claims abstract description 23
- 239000000463 material Substances 0.000 claims abstract description 22
- 238000001035 drying Methods 0.000 claims abstract description 21
- 238000005406 washing Methods 0.000 claims abstract description 20
- KYWMCFOWDYFYLV-UHFFFAOYSA-N 1h-imidazole-2-carboxylic acid Chemical compound OC(=O)C1=NC=CN1 KYWMCFOWDYFYLV-UHFFFAOYSA-N 0.000 claims abstract description 17
- 238000001914 filtration Methods 0.000 claims abstract description 13
- 230000003197 catalytic effect Effects 0.000 claims abstract description 10
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 claims abstract description 10
- 238000007112 amidation reaction Methods 0.000 claims abstract description 9
- 238000005886 esterification reaction Methods 0.000 claims abstract description 9
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- 238000007306 functionalization reaction Methods 0.000 claims abstract description 5
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- 239000008367 deionised water Substances 0.000 claims description 10
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- PHQOGHDTIVQXHL-UHFFFAOYSA-N n'-(3-trimethoxysilylpropyl)ethane-1,2-diamine Chemical compound CO[Si](OC)(OC)CCCNCCN PHQOGHDTIVQXHL-UHFFFAOYSA-N 0.000 claims description 10
- 238000001132 ultrasonic dispersion Methods 0.000 claims description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 claims description 10
- 238000006243 chemical reaction Methods 0.000 claims description 9
- 150000001868 cobalt Chemical class 0.000 claims description 9
- 150000002815 nickel Chemical class 0.000 claims description 9
- 150000003751 zinc Chemical class 0.000 claims description 9
- 239000003054 catalyst Substances 0.000 claims description 8
- QYIGOGBGVKONDY-UHFFFAOYSA-N 1-(2-bromo-5-chlorophenyl)-3-methylpyrazole Chemical compound N1=C(C)C=CN1C1=CC(Cl)=CC=C1Br QYIGOGBGVKONDY-UHFFFAOYSA-N 0.000 claims description 7
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- 238000001354 calcination Methods 0.000 claims description 7
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- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims description 7
- 238000002156 mixing Methods 0.000 claims description 7
- 239000000203 mixture Substances 0.000 claims description 6
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims description 6
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims description 5
- 229910001981 cobalt nitrate Inorganic materials 0.000 claims description 5
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 claims description 5
- MQRWBMAEBQOWAF-UHFFFAOYSA-N acetic acid;nickel Chemical compound [Ni].CC(O)=O.CC(O)=O MQRWBMAEBQOWAF-UHFFFAOYSA-N 0.000 claims description 4
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 claims description 4
- 229940011182 cobalt acetate Drugs 0.000 claims description 4
- 229910000361 cobalt sulfate Inorganic materials 0.000 claims description 4
- 229940044175 cobalt sulfate Drugs 0.000 claims description 4
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 claims description 4
- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical compound [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 claims description 4
- 229940078494 nickel acetate Drugs 0.000 claims description 4
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 claims description 4
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 claims description 4
- 239000011701 zinc Substances 0.000 claims description 4
- 239000004246 zinc acetate Substances 0.000 claims description 4
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 claims description 4
- 229910000368 zinc sulfate Inorganic materials 0.000 claims description 4
- 229960001763 zinc sulfate Drugs 0.000 claims description 4
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 claims description 3
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 claims description 3
- 238000007598 dipping method Methods 0.000 claims description 3
- 239000007788 liquid Substances 0.000 claims description 3
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 claims description 3
- 239000011592 zinc chloride Substances 0.000 claims description 3
- 235000005074 zinc chloride Nutrition 0.000 claims description 3
- 229910021536 Zeolite Inorganic materials 0.000 abstract description 5
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 abstract description 5
- 239000010457 zeolite Substances 0.000 abstract description 5
- 238000002791 soaking Methods 0.000 abstract description 4
- 239000003795 chemical substances by application Substances 0.000 abstract 1
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- 239000011148 porous material Substances 0.000 description 5
- 239000013153 zeolitic imidazolate framework Substances 0.000 description 5
- OOCCDEMITAIZTP-QPJJXVBHSA-N (E)-cinnamyl alcohol Chemical compound OC\C=C\C1=CC=CC=C1 OOCCDEMITAIZTP-QPJJXVBHSA-N 0.000 description 4
- 238000011065 in-situ storage Methods 0.000 description 4
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 3
- KJPRLNWUNMBNBZ-QPJJXVBHSA-N (E)-cinnamaldehyde Chemical compound O=C\C=C\C1=CC=CC=C1 KJPRLNWUNMBNBZ-QPJJXVBHSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
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- AXMVYSVVTMKQSL-UHFFFAOYSA-N UNPD142122 Natural products OC1=CC=C(C=CC=O)C=C1O AXMVYSVVTMKQSL-UHFFFAOYSA-N 0.000 description 1
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- 230000009435 amidation Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052797 bismuth Inorganic materials 0.000 description 1
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- ZCDOYSPFYFSLEW-UHFFFAOYSA-N chromate(2-) Chemical compound [O-][Cr]([O-])(=O)=O ZCDOYSPFYFSLEW-UHFFFAOYSA-N 0.000 description 1
- KRVSOGSZCMJSLX-UHFFFAOYSA-L chromic acid Substances O[Cr](O)(=O)=O KRVSOGSZCMJSLX-UHFFFAOYSA-L 0.000 description 1
- 229940117916 cinnamic aldehyde Drugs 0.000 description 1
- KJPRLNWUNMBNBZ-UHFFFAOYSA-N cinnamic aldehyde Natural products O=CC=CC1=CC=CC=C1 KJPRLNWUNMBNBZ-UHFFFAOYSA-N 0.000 description 1
- 230000000536 complexating effect Effects 0.000 description 1
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- 238000000151 deposition Methods 0.000 description 1
- AWJWCTOOIBYHON-UHFFFAOYSA-N furo[3,4-b]pyrazine-5,7-dione Chemical compound C1=CN=C2C(=O)OC(=O)C2=N1 AWJWCTOOIBYHON-UHFFFAOYSA-N 0.000 description 1
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- JBFYUZGYRGXSFL-UHFFFAOYSA-N imidazolide Chemical compound C1=C[N-]C=N1 JBFYUZGYRGXSFL-UHFFFAOYSA-N 0.000 description 1
- 125000002883 imidazolyl group Chemical group 0.000 description 1
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- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
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- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
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- 239000002351 wastewater Substances 0.000 description 1
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- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 1
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Abstract
本发明公开一种纳米铬酸铋/g‑C3N4改性MOFs复合材料制备方法及其应用,所述MOFs材料为类沸石咪唑酯骨架材料,以咪唑‑2‑甲酸为有机配体,以Zn2+、Ni2+、Co2+为无机配体,通过酰胺化反应及酯化反应与功能化g‑C3N4接枝共聚,负载纳米铬酸铋催化剂,包括以下步骤:S1:制备功能化g‑C3N4;S2:制备无机配体溶液;S3:制备有机配体溶液;S4:制备g‑C3N4改性MOFs复合材料;S5:将所得g‑C3N4改性MOFs复合材料加入0.15~0.2mol/L K2CrO4溶液中,浸渍吸附0.5~3h,再滴加乙酸铋‑盐酸溶液,25℃室温下,搅拌反应1~6h,过滤、洗涤、干燥,即得。本发明改性MOFs复合材料具有三维沸石拓扑结构、高孔隙率、高稳定性、高催化活性特点,高效分离光生电子和空穴,应用于催化氧化芳香醇制芳香醛。
Description
技术领域
本发明属于MOFs功能化改性领域,具体涉及一种纳米铬酸铋/g-C3N4改性MOFs复合材料制备方法及其应用。
背景技术
金属-有机骨架材料,是由过渡金属离子与羧酸类或含氮类有机多齿配体通过配位作用自主装形成具有周期性的多维网状结构的一类新型多孔材料,具有高孔隙率、低密度、大比表面积、孔道规则、孔径可调以及拓扑结构多样性和可裁剪性等优点。MOFs材料兼具无机材料刚性和有机材料柔韧性的特征,在气体的存储、催化剂、分离、吸附以及光电磁材料中具有重要应用,同时,由于MOFs材料具有大量不饱和金属位,具有高度的分子选择性。类沸石咪唑酯骨架材料简称ZIFs,是由二价过渡族金属离子与咪唑基配体络合后形成的一种具有沸石拓扑结构的新型MOFs材料。ZIFs材料不仅具有传统MOFs材料的优点,而且具有无机沸石的高稳定性,其热稳性达到550℃,耐热碱和有机溶剂等,还可以通过调节金属离子与有机配体获得不同的结构和功能。
纳米铬酸铋是一种新型铬酸盐光催化剂,具有非常宽的光谱吸收范围,可将吸收带边拓展至610nm的红光区,其禁带宽度为2.03eV,远低于传统TiO2光催化剂的3.0~3.2eV,对可见光具有良好的响应能力,同时,其光电压响应范围也可拓展至红光区,表现出优异的光生电子与光生空穴的分离效率,因此,铬酸铋具有优异的可见光催化性质。目前,关于纳米铬酸铋的研究及应用还较为罕见,仅三例报道,具体为:申请号为CN201711286334.X的专利,公开一种高活性铬酸铋纳米光催化剂的制备方法及其应用;申请号为CN202010883227.0的专利,公开一种复合光催化剂在染料废水处理中的应用;申请号为CN00818717.7的专利,公开补充促进剂与碳担载的含贵金属的催化剂一起在液相氧化反应中的用途;但利用纳米铬酸铋与MOFs材料尤其是与ZIFs材料复合研发新型催化剂还未有相关资料报道,是新材料领域的空白。
因此,本发明公开一种纳米铬酸铋/g-C3N4改性MOFs复合材料制备方法及其在催化氧化芳香醇制芳香醛中的应用,以MOFs材料为载体,接枝g-C3N4,并进一步原位生长纳米铬酸铋;该MOFs材料为类沸石咪唑酯骨架材料,以咪唑-2-甲酸为有机配体,以Zn2+、Ni2+、Co2+为无机配体,通过酰胺化反应及酯化反应与富-OH及-NH2的功能化g-C3N4接枝共聚,再通过化学沉淀法原位沉积纳米铬酸铋催化剂,合成的新型异质结催化剂可高选择性地催化氧化醇成醛。
发明内容
针对现有技术的不足之处,本发明的目的在于提供一种纳米铬酸铋/g-C3N4改性MOFs复合材料制备方法及其应用。
本发明的技术方案概述如下:
一种纳米铬酸铋/g-C3N4改性MOFs复合材料制备方法,所述MOFs材料为类沸石咪唑酯骨架材料,以咪唑-2-甲酸为有机配体,以Zn2+、Ni2+、Co2+为无机配体,通过酰胺化反应及酯化反应与功能化g-C3N4接枝共聚,负载纳米铬酸铋催化剂,包括以下步骤:
S1:将纳米g-C3N4加入去离子水中,超声分散后,加入乙醇胺、N-2-(氨乙基)-3-氨丙基三甲氧基硅烷,搅拌均匀后,80~100℃水热反应0.5~2h,离心、洗涤、干燥后,得功能化g-C3N4;
S2:将锌盐、镍盐、钴盐加入体积浓度为75%乙醇溶液中,50℃搅拌溶解后,得到无机配体溶液;
S3:将咪唑-2-甲酸溶解于DMF中,得到有机配体溶液;
S4:将无机配体溶液和有机配体溶液混合均匀后,加入功能化g-C3N4和EDC·HCL,超声分散后,移至反应釜中,100~160℃溶剂热条件下,搅拌反应12~36h,冷却至室温,过滤、洗涤、干燥,即得g-C3N4改性MOFs复合材料;
S5:将所得g-C3N4改性MOFs复合材料加入0.15~0.2mol/L K2CrO4溶液中,浸渍吸附0.5~3h,再滴加乙酸铋-盐酸溶液,25℃室温下,搅拌反应1~6h,过滤、洗涤、干燥,即得所述纳米铬酸铋/g-C3N4改性MOFs复合材料。
优选的是,所述锌盐为硝酸锌、醋酸锌、氯化锌、硫酸锌中的一种或多种。
优选的是,所述镍盐为硝酸镍、醋酸镍、氯化镍、硫酸镍中的一种或多种。
优选的是,所述钴盐为硝酸钴、醋酸钴、氯化钴、硫酸钴中的一种或多种。
优选的是,所述乙酸铋-盐酸溶液制备方法为:将乙酸铋加入0.05mol/L稀HCl溶液中,控制用量比为(0.6~1)mmol:10mL,40~60℃搅拌溶解,即得乙酸铋-盐酸溶液,4℃保存备用。
优选的是,所述纳米g-C3N4的制备方法为:将三聚氰胺加入无水乙醇中,控制固液比为0.5g/mL,超声溶解后,90~150℃蒸发乙醇后,再置于马弗炉中加热至550~600℃,恒温煅烧4~6h,充分研磨后,即得纳米g-C3N4。
优选的是,所述纳米g-C3N4、去离子水、乙醇胺、N-2-(氨乙基)-3-氨丙基三甲氧基硅烷用量比为1g:10mL:(0.2~0.4)g:(0.3~0.6)mL。
优选的是,S2~S4中,所述锌盐、镍盐、钴盐、乙醇溶液、咪唑-2-甲酸、DMF、功能化g-C3N4、EDC·HCL用量比为(2~10)mmol:(2~10)mmol:(1~5)mmol:20mL:(20~30)mmol:20mL:(0.2~0.8)g:(0.2~0.3)g。
优选的是,所述g-C3N4改性MOFs复合材料、K2CrO4溶液、乙酸铋-盐酸溶液用量比为2g:(10~15)mL:(10~15)mL。
一种纳米铬酸铋/g-C3N4改性MOFs复合材料在催化氧化芳香醇制芳香醛中的应用。
本发明的有益效果:
1、本发明首次以咪唑-2-甲酸为有机配体,以Zn2+、Ni2+、Co2+为无机配体,通过酰胺化反应及酯化反应与富氨基、羟基功能化g-C3N4接枝共聚,再通过化学沉淀法原位沉积纳米铬酸铋,合成具有三维沸石拓扑结构、高孔隙率、高稳定性、高催化活性的纳米铬酸铋/g-C3N4改性MOFs复合材料,应用于催化氧化芳香醇制芳香醛。
2、本发明利用酰胺化反应及酯化反应将富氨基、羟基的功能化g-C3N4接枝到MOFs骨架结构中,通过化学键实现分子内键合,显著提高氧化石墨烯改性MOFs的结构稳定性。
3、本发明通过利用化学沉淀法实现纳米铬酸铋与g-C3N4改性MOFs复合材料的结合,由于三者的费米能级不同,形成异质结结构,改变电子的传递路径,g-C3N4和MOFs作为电荷传输介质,使光生电子自发地从纳米铬酸铋晶面转移到g-C3N4和MOFs的导带,高效分离光生电子和空穴,使空穴积累在纳米铬酸铋上,显著提高光催化氧化能力;MOFs具有发达的孔道结构和高比面积,为纳米铬酸铋量子点提供了充足的生长位点,避免了纳米铬酸铋间的团聚,使其保持良好的表面效应和量子尺寸。
附图说明
图1为本发明纳米铬酸铋/g-C3N4改性MOFs复合材料制备方法流程图。
具体实施方式
下面结合实施例对本发明做进一步的详细说明,以令本领域技术人员参照说明书文字能够据以实施。
本发明提供一实施例的纳米铬酸铋/g-C3N4改性MOFs复合材料制备方法,所述MOFs材料为类沸石咪唑酯骨架材料,以咪唑-2-甲酸为有机配体,以Zn2+、Ni2+、Co2+为无机配体,通过酰胺化反应及酯化反应与功能化g-C3N4接枝共聚,负载纳米铬酸铋催化剂,包括以下步骤:
S1:将三聚氰胺加入无水乙醇中,控制固液比为0.5g/mL,超声溶解后,90~150℃蒸发乙醇后,再置于马弗炉中加热至550~600℃,恒温煅烧4~6h,充分研磨后,即得纳米g-C3N4;
S2:将纳米g-C3N4加入去离子水中,超声分散后,加入乙醇胺、N-2-(氨乙基)-3-氨丙基三甲氧基硅烷,控制纳米g-C3N4、去离子水、乙醇胺、N-2-(氨乙基)-3-氨丙基三甲氧基硅烷用量比为1g:10mL:(0.2~0.4)g:(0.3~0.6)mL,搅拌均匀后,80~100℃水热反应0.5~2h,离心、洗涤、干燥后,得功能化g-C3N4;
S3:将锌盐、镍盐、钴盐加入体积浓度为75%乙醇溶液中,50℃搅拌溶解后,得到无机配体溶液;所述锌盐为硝酸锌、醋酸锌、氯化锌、硫酸锌中的一种或多种;所述镍盐为硝酸镍、醋酸镍、氯化镍、硫酸镍中的一种或多种;所述钴盐为硝酸钴、醋酸钴、氯化钴、硫酸钴中的一种或多种;
S4:将咪唑-2-甲酸溶解于DMF中,得到有机配体溶液;
S5:将无机配体溶液和有机配体溶液混合均匀后,加入功能化g-C3N4和EDC·HCL,超声分散后,移至反应釜中,100~160℃溶剂热条件下,搅拌反应12~36h,冷却至室温,过滤、洗涤、干燥,即得g-C3N4改性MOFs复合材料;
所述锌盐、镍盐、钴盐、乙醇溶液、咪唑-2-甲酸、DMF、功能化g-C3N4、EDC·HCL用量比为(2~10)mmol:(2~10)mmol:(1~5)mmol:20mL:(20~30)mmol:20mL:(0.2~0.8)g:(0.2~0.3)g;
S6:将乙酸铋加入0.05mol/L稀HCl溶液中,控制用量比为(0.6~1)mmol:10mL,40~60℃搅拌溶解,即得乙酸铋-盐酸溶液,4℃保存备用;
S7:将所得g-C3N4改性MOFs复合材料加入0.15~0.2mol/L K2CrO4溶液中,浸渍吸附0.5~3h,再滴加乙酸铋-盐酸溶液,控制g-C3N4改性MOFs复合材料、K2CrO4溶液、乙酸铋-盐酸溶液用量比为2g:(10~15)mL:(10~15)mL,25℃室温下,搅拌反应1~6h,过滤、洗涤、干燥,即得所述纳米铬酸铋/g-C3N4改性MOFs复合材料。
本发明进一步提供该实施例的纳米铬酸铋/g-C3N4改性MOFs复合材料在催化氧化芳香醇制芳香醛中的应用。
实施例1
一种纳米铬酸铋/g-C3N4改性MOFs复合材料制备方法,,包括以下步骤:
S1:将10g三聚氰胺加入20mL无水乙醇中,超声溶解后,90℃蒸发乙醇后,再置于马弗炉中加热至550℃,恒温煅烧4h,充分研磨后,即得纳米g-C3N4;
S2:将1g纳米g-C3N4加入10mL去离子水中,超声分散后,加入0.2g乙醇胺、0.3mL N-2-(氨乙基)-3-氨丙基三甲氧基硅烷,搅拌均匀后,80℃水热反应0.5h,离心、洗涤、干燥后,得功能化g-C3N4;
S3:将2mmol硝酸锌、2mmol硝酸镍、1mmol硝酸钴加入20mL体积浓度为75%乙醇溶液中,50℃搅拌溶解后,得到无机配体溶液;
S4:将20mmol咪唑-2-甲酸溶解于20mL DMF中,得到有机配体溶液;
S5:将S3所得无机配体溶液和S4所得有机配体溶液混合均匀后,加入0.2g功能化g-C3N4和0.2g EDC·HCL,超声分散后,移至反应釜中,100℃溶剂热条件下,搅拌反应24h,冷却至室温,过滤、洗涤、干燥,即得g-C3N4改性MOFs复合材料;
S6:将1.2mmol乙酸铋加入20mL的0.05mol/L稀HCl溶液中,40℃搅拌溶解,即得乙酸铋-盐酸溶液,4℃保存备用;
S7:将2g的g-C3N4改性MOFs复合材料加入10mL的0.15mol/L K2CrO4溶液中,浸渍吸附1h,再滴加10mL乙酸铋-盐酸溶液,25℃室温下,搅拌反应1h,过滤、洗涤、干燥,即得所述纳米铬酸铋/g-C3N4改性MOFs复合材料。
实施例2
一种纳米铬酸铋/g-C3N4改性MOFs复合材料制备方法,,包括以下步骤:
S1:将10g三聚氰胺加入20mL无水乙醇中,超声溶解后120℃蒸发乙醇后,再置于马弗炉中加热至550℃,恒温煅烧5h,充分研磨后,即得纳米g-C3N4;
S2:将1g纳米g-C3N4加入10mL去离子水中,超声分散后,加入0.3g乙醇胺、0.5mL N-2-(氨乙基)-3-氨丙基三甲氧基硅烷,搅拌均匀后,90℃水热反应1h,离心、洗涤、干燥后,得功能化g-C3N4;
S3:将6mmol醋酸锌、6mmol醋酸镍、3mmol醋酸钴加入20mL体积浓度为75%乙醇溶液中,50℃搅拌溶解后,得到无机配体溶液;
S4:将25mmol咪唑-2-甲酸溶解于20mL DMF中,得到有机配体溶液;
S5:将S3所得无机配体溶液和S4所得有机配体溶液混合均匀后,加入0.5g功能化g-C3N4和0.25g EDC·HCL,超声分散后,移至反应釜中,130℃溶剂热条件下,搅拌反应30h,冷却至室温,过滤、洗涤、干燥,即得g-C3N4改性MOFs复合材料;
S6:将1.6mmol乙酸铋加入20mL的0.05mol/L稀HCl溶液中,40~60℃搅拌溶解,即得乙酸铋-盐酸溶液,4℃保存备用;
S7:将2g的g-C3N4改性MOFs复合材料加入12.5mL的0.18mol/L K2CrO4溶液中,浸渍吸附2h,再滴加12.5mL乙酸铋-盐酸溶液,25℃室温下,搅拌反应3h,过滤、洗涤、干燥,即得所述纳米铬酸铋/g-C3N4改性MOFs复合材料。
实施例3
一种纳米铬酸铋/g-C3N4改性MOFs复合材料制备方法,,包括以下步骤:
S1:将10g三聚氰胺加入20mL无水乙醇中,超声溶解后,150℃蒸发乙醇后,再置于马弗炉中加热至600℃,恒温煅烧6h,充分研磨后,即得纳米g-C3N4;
S2:将1g纳米g-C3N4加入10mL去离子水中,超声分散后,加入0.4g乙醇胺、0.6mL N-2-(氨乙基)-3-氨丙基三甲氧基硅烷,搅拌均匀后,100℃水热反应2h,离心、洗涤、干燥后,得功能化g-C3N4;
S3:将10mmol硫酸锌、10mmol硫酸镍、5mmol硫酸钴加入20mL体积浓度为75%乙醇溶液中,50℃搅拌溶解后,得到无机配体溶液;
S4:将20~30mmol咪唑-2-甲酸溶解于20mL DMF中,得到有机配体溶液;
S5:将S3所得无机配体溶液和S4所得有机配体溶液混合均匀后,加入0.8g功能化g-C3N4和0.3g EDC·HCL,超声分散后,移至反应釜中,160℃溶剂热条件下,搅拌反应36h,冷却至室温,过滤、洗涤、干燥,即得g-C3N4改性MOFs复合材料;
S6:将2mmol乙酸铋加入20mL的0.05mol/L稀HCl溶液中,60℃搅拌溶解,即得乙酸铋-盐酸溶液,4℃保存备用;
S7:将2g的g-C3N4改性MOFs复合材料加入15mL的0.2mol/L K2CrO4溶液中,浸渍吸附3h,再滴加15mL乙酸铋-盐酸溶液,25℃室温下,搅拌反应6h,过滤、洗涤、干燥,即得所述纳米铬酸铋/g-C3N4改性MOFs复合材料。
对比例1以g-C3N4改性MOFs复合材料,制备方法包括以下步骤:
一种纳米铬酸铋/g-C3N4改性MOFs复合材料制备方法,,包括以下步骤:
S1:将10g三聚氰胺加入20mL无水乙醇中,超声溶解后,90℃蒸发乙醇后,再置于马弗炉中加热至550℃,恒温煅烧4h,充分研磨后,即得纳米g-C3N4;
S2:将1g纳米g-C3N4加入10mL去离子水中,超声分散后,加入0.2g乙醇胺、0.3mL N-2-(氨乙基)-3-氨丙基三甲氧基硅烷,搅拌均匀后,80℃水热反应0.5h,离心、洗涤、干燥后,得功能化g-C3N4;
S3:将2mmol硝酸锌、2mmol硝酸镍、1mmol硝酸钴加入20mL体积浓度为75%乙醇溶液中,50℃搅拌溶解后,得到无机配体溶液;
S4:将20mmol咪唑-2-甲酸溶解于20mL DMF中,得到有机配体溶液;
S5:将S3所得无机配体溶液和S4所得有机配体溶液混合均匀后,加入0.2g功能化g-C3N4和0.2g EDC·HCL,超声分散后,移至反应釜中,100℃溶剂热条件下,搅拌反应24h,冷却至室温,过滤、洗涤、干燥,即得g-C3N4改性MOFs复合材料。
采用实施例1~3及对比例1制备出的复合材料催化氧化肉桂醇生成肉桂醛,试验方法如下:
将20mg复合材料加入20mL N,N-二甲基甲酰胺,超声分散后,制成悬液;
将0.5mmol肉桂醇加入到悬液中,搅拌均匀,打开氙灯灯源,控制光辐射密度为200mW/cm2;
反应3h后,离心取上清液,对其进行GC-MS、GC定性、定量分析。
试验结果如下表所示:
实施例1 | 实施例2 | 实施例3 | 对比例1 | |
转化率/% | 58.1 | 60.6 | 63.4 | 24.7 |
肉桂醛选择性/% | 96.8 | 97.5 | 97.2 | 92.9 |
产率/% | 55.7 | 58.4 | 61.6 | 22.1 |
实施例1~3首次以咪唑-2-甲酸为有机配体,以Zn2+、Ni2+、Co2+为无机配体,通过酰胺化反应及酯化反应与富氨基、羟基功能化g-C3N4接枝共聚,再通过化学沉淀法原位沉积纳米铬酸铋,合成具有三维沸石拓扑结构、高孔隙率、高稳定性、高催化活性的纳米铬酸铋/g-C3N4改性MOFs复合材料,应用于催化氧化芳香醇制芳香醛。
实施例1~3利用酰胺化反应及酯化反应将富氨基、羟基的功能化g-C3N4接枝到MOFs骨架结构中,通过化学键实现分子内键合,显著提高氧化石墨烯改性MOFs的结构稳定性。
实施例1~3通过利用化学沉淀法实现纳米铬酸铋与g-C3N4改性MOFs复合材料的结合,由于三者的费米能级不同,形成异质结结构,改变电子的传递路径,g-C3N4和MOFs作为电荷传输介质,使光生电子自发地从纳米铬酸铋晶面转移到g-C3N4和MOFs的导带,高效分离光生电子和空穴,使空穴积累在纳米铬酸铋上,使光生电子积累在g-C3N4和MOFs上,显著提高光催化氧化还原能力;MOFs具有发达的孔道结构和高比面积,为纳米铬酸铋量子点提供了充足的生长位点,避免了纳米铬酸铋间的团聚,使其保持良好的表面效应和量子尺寸。
尽管本发明的实施方案已公开如上,但其并不仅仅限于说明书和实施方式中所列运用,它完全可以被适用于各种适合本发明的领域,对于熟悉本领域的人员而言,可容易地实现另外的修改,因此在不背离权利要求及等同范围所限定的一般概念下,本发明并不限于特定的细节。
Claims (10)
1.一种纳米铬酸铋/g-C3N4改性MOFs复合材料制备方法,其特征在于,所述MOFs材料为类沸石咪唑酯骨架材料,以咪唑-2-甲酸为有机配体,以Zn2+、Ni2+、Co2+为无机配体,通过酰胺化反应及酯化反应与功能化g-C3N4接枝共聚,负载纳米铬酸铋催化剂,包括以下步骤:
S1:将纳米g-C3N4加入去离子水中,超声分散后,加入乙醇胺、N-2-(氨乙基)-3-氨丙基三甲氧基硅烷,搅拌均匀后,80~100℃水热反应0.5~2h,离心、洗涤、干燥后,得功能化g-C3N4;
S2:将锌盐、镍盐、钴盐加入体积浓度为75%乙醇溶液中,50℃搅拌溶解后,得到无机配体溶液;
S3:将咪唑-2-甲酸溶解于DMF中,得到有机配体溶液;
S4:将无机配体溶液和有机配体溶液混合均匀后,加入功能化g-C3N4和EDC·HCL,超声分散后,移至反应釜中,100~160℃溶剂热条件下,搅拌反应12~36h,冷却至室温,过滤、洗涤、干燥,即得g-C3N4改性MOFs复合材料;
S5:将所得g-C3N4改性MOFs复合材料加入0.15~0.2mol/L K2CrO4溶液中,浸渍吸附0.5~3h,再滴加乙酸铋-盐酸溶液,25℃室温下,搅拌反应1~6h,过滤、洗涤、干燥,即得所述纳米铬酸铋/g-C3N4改性MOFs复合材料。
2.根据权利要求1所述一种纳米铬酸铋/g-C3N4改性MOFs复合材料制备方法,其特征在于,所述锌盐为硝酸锌、醋酸锌、氯化锌、硫酸锌中的一种或多种。
3.根据权利要求1所述一种纳米铬酸铋/g-C3N4改性MOFs复合材料制备方法,其特征在于,所述镍盐为硝酸镍、醋酸镍、氯化镍、硫酸镍中的一种或多种。
4.根据权利要求1所述一种纳米铬酸铋/g-C3N4改性MOFs复合材料制备方法,其特征在于,所述钴盐为硝酸钴、醋酸钴、氯化钴、硫酸钴中的一种或多种。
5.根据权利要求1所述一种纳米铬酸铋/g-C3N4改性MOFs复合材料制备方法,其特征在于,所述乙酸铋-盐酸溶液制备方法为:将乙酸铋加入0.05mol/L稀HCl溶液中,控制用量比为(0.6~1)mmol:10mL,40~60℃搅拌溶解,即得乙酸铋-盐酸溶液,4℃保存备用。
6.根据权利要求1所述一种纳米铬酸铋/g-C3N4改性MOFs复合材料制备方法,其特征在于,所述纳米g-C3N4的制备方法为:将三聚氰胺加入无水乙醇中,控制固液比为0.5g/mL,超声溶解后,90~150℃蒸发乙醇后,再置于马弗炉中加热至550~600℃,恒温煅烧4~6h,充分研磨后,即得纳米g-C3N4。
7.根据权利要求1所述一种纳米铬酸铋/g-C3N4改性MOFs复合材料制备方法,其特征在于,所述纳米g-C3N4、去离子水、乙醇胺、N-2-(氨乙基)-3-氨丙基三甲氧基硅烷用量比为1g:10mL:(0.2~0.4)g:(0.3~0.6)mL。
8.根据权利要求1所述一种纳米铬酸铋/g-C3N4改性MOFs复合材料制备方法,其特征在于,S2~S4中,所述锌盐、镍盐、钴盐、乙醇溶液、咪唑-2-甲酸、DMF、功能化g-C3N4、EDC·HCL用量比为(2~10)mmol:(2~10)mmol:(1~5)mmol:20mL:(20~30)mmol:20mL:(0.2~0.8)g:(0.2~0.3)g。
9.根据权利要求1所述一种纳米铬酸铋/g-C3N4改性MOFs复合材料制备方法,其特征在于,所述g-C3N4改性MOFs复合材料、K2CrO4溶液、乙酸铋-盐酸溶液用量比为2g:(10~15)mL:(10~15)mL。
10.如权利要求1~9任一项所述的一种纳米铬酸铋/g-C3N4改性MOFs复合材料在催化氧化芳香醇制芳香醛中的应用。
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CN116328743B (zh) * | 2023-05-11 | 2024-05-07 | 北京工业大学 | 一种在斜发沸石表面原位生长微晶的复合材料制备方法 |
CN116675223A (zh) * | 2023-08-03 | 2023-09-01 | 国联汽车动力电池研究院有限责任公司 | 多孔复合负极材料及其制备方法、低温电池 |
CN116675223B (zh) * | 2023-08-03 | 2023-11-28 | 国联汽车动力电池研究院有限责任公司 | 多孔复合负极材料及其制备方法、低温电池 |
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