CN114570429B - 一种单原子负载共价有机框架材料及其制备与在光解水制氢中的应用 - Google Patents
一种单原子负载共价有机框架材料及其制备与在光解水制氢中的应用 Download PDFInfo
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- CN114570429B CN114570429B CN202011376361.8A CN202011376361A CN114570429B CN 114570429 B CN114570429 B CN 114570429B CN 202011376361 A CN202011376361 A CN 202011376361A CN 114570429 B CN114570429 B CN 114570429B
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- 239000013310 covalent-organic framework Substances 0.000 title claims abstract description 80
- 239000000463 material Substances 0.000 title claims abstract description 60
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 40
- 239000001257 hydrogen Substances 0.000 title claims abstract description 39
- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 39
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title claims abstract description 37
- 238000006303 photolysis reaction Methods 0.000 title claims abstract description 11
- 230000015843 photosynthesis, light reaction Effects 0.000 title claims abstract description 11
- 238000004519 manufacturing process Methods 0.000 title claims description 19
- 238000002360 preparation method Methods 0.000 title abstract description 16
- 239000002904 solvent Substances 0.000 claims abstract description 28
- 229910052751 metal Inorganic materials 0.000 claims abstract description 16
- 239000002184 metal Substances 0.000 claims abstract description 16
- 238000000034 method Methods 0.000 claims abstract description 16
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 54
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 46
- 238000006243 chemical reaction Methods 0.000 claims description 29
- 239000002243 precursor Substances 0.000 claims description 26
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 18
- 235000019441 ethanol Nutrition 0.000 claims description 17
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 16
- 239000003054 catalyst Substances 0.000 claims description 16
- 239000000243 solution Substances 0.000 claims description 15
- 239000012046 mixed solvent Substances 0.000 claims description 13
- RFFLAFLAYFXFSW-UHFFFAOYSA-N 1,2-dichlorobenzene Chemical compound ClC1=CC=CC=C1Cl RFFLAFLAYFXFSW-UHFFFAOYSA-N 0.000 claims description 12
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 12
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 12
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 12
- RDOXTESZEPMUJZ-UHFFFAOYSA-N anisole Chemical compound COC1=CC=CC=C1 RDOXTESZEPMUJZ-UHFFFAOYSA-N 0.000 claims description 12
- 238000003756 stirring Methods 0.000 claims description 12
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims description 11
- 239000007864 aqueous solution Substances 0.000 claims description 11
- 238000001914 filtration Methods 0.000 claims description 11
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 10
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 9
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 claims description 8
- AUHZEENZYGFFBQ-UHFFFAOYSA-N mesitylene Substances CC1=CC(C)=CC(C)=C1 AUHZEENZYGFFBQ-UHFFFAOYSA-N 0.000 claims description 8
- 125000001827 mesitylenyl group Chemical group [H]C1=C(C(*)=C(C([H])=C1C([H])([H])[H])C([H])([H])[H])C([H])([H])[H] 0.000 claims description 8
- 230000003287 optical effect Effects 0.000 claims description 8
- -1 (2- (methylthio) ethoxy) terephthalate Chemical compound 0.000 claims description 7
- 239000002253 acid Substances 0.000 claims description 7
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- 238000001816 cooling Methods 0.000 claims description 7
- 238000005406 washing Methods 0.000 claims description 7
- OYFRNYNHAZOYNF-UHFFFAOYSA-N 2,5-dihydroxyterephthalic acid Chemical compound OC(=O)C1=CC(O)=C(C(O)=O)C=C1O OYFRNYNHAZOYNF-UHFFFAOYSA-N 0.000 claims description 6
- WVDDGKGOMKODPV-UHFFFAOYSA-N Benzyl alcohol Chemical compound OCC1=CC=CC=C1 WVDDGKGOMKODPV-UHFFFAOYSA-N 0.000 claims description 6
- QMMFVYPAHWMCMS-UHFFFAOYSA-N Dimethyl sulfide Chemical compound CSC QMMFVYPAHWMCMS-UHFFFAOYSA-N 0.000 claims description 6
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 6
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 6
- 239000003377 acid catalyst Substances 0.000 claims description 6
- 239000003638 chemical reducing agent Substances 0.000 claims description 6
- 238000007872 degassing Methods 0.000 claims description 6
- UQOUOXLHXPHDHF-UHFFFAOYSA-N diethyl 2,5-dihydroxybenzene-1,4-dicarboxylate Chemical compound CCOC(=O)C1=CC(O)=C(C(=O)OCC)C=C1O UQOUOXLHXPHDHF-UHFFFAOYSA-N 0.000 claims description 6
- 239000007788 liquid Substances 0.000 claims description 6
- UZKWTJUDCOPSNM-UHFFFAOYSA-N methoxybenzene Substances CCCCOC=C UZKWTJUDCOPSNM-UHFFFAOYSA-N 0.000 claims description 6
- 229910052757 nitrogen Inorganic materials 0.000 claims description 6
- 229910052700 potassium Inorganic materials 0.000 claims description 6
- 239000011591 potassium Substances 0.000 claims description 6
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 6
- 238000002791 soaking Methods 0.000 claims description 6
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 6
- 238000010257 thawing Methods 0.000 claims description 6
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims description 5
- 125000004177 diethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 5
- 229910052724 xenon Inorganic materials 0.000 claims description 5
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 claims description 5
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 4
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 4
- 238000007605 air drying Methods 0.000 claims description 4
- 235000010323 ascorbic acid Nutrition 0.000 claims description 4
- 229960005070 ascorbic acid Drugs 0.000 claims description 4
- 239000011668 ascorbic acid Substances 0.000 claims description 4
- XWDKRVSSHIJNJP-UHFFFAOYSA-N carbon monoxide;iridium Chemical group [Ir].[Ir].[Ir].[Ir].[O+]#[C-].[O+]#[C-].[O+]#[C-].[O+]#[C-].[O+]#[C-].[O+]#[C-].[O+]#[C-].[O+]#[C-].[O+]#[C-].[O+]#[C-].[O+]#[C-].[O+]#[C-] XWDKRVSSHIJNJP-UHFFFAOYSA-N 0.000 claims description 4
- 238000007710 freezing Methods 0.000 claims description 4
- 230000008014 freezing Effects 0.000 claims description 4
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 claims description 4
- 238000010992 reflux Methods 0.000 claims description 4
- 238000007789 sealing Methods 0.000 claims description 4
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims description 4
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 claims description 3
- MYFKLQFBFSHBPA-UHFFFAOYSA-N 1-chloro-2-methylsulfanylethane Chemical compound CSCCCl MYFKLQFBFSHBPA-UHFFFAOYSA-N 0.000 claims description 3
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 3
- 238000004140 cleaning Methods 0.000 claims description 3
- 229910017052 cobalt Inorganic materials 0.000 claims description 3
- 239000010941 cobalt Substances 0.000 claims description 3
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 3
- 150000004687 hexahydrates Chemical class 0.000 claims description 3
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 claims description 3
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 3
- 239000000126 substance Substances 0.000 claims description 3
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 3
- PAGZTSLSNQZYEV-UHFFFAOYSA-L 2,2-dimethylpropanoate;palladium(2+) Chemical compound [Pd+2].CC(C)(C)C([O-])=O.CC(C)(C)C([O-])=O PAGZTSLSNQZYEV-UHFFFAOYSA-L 0.000 claims description 2
- OZHLXQFAHIYYDJ-UHFFFAOYSA-L 2-hydroxyacetate;nickel(2+) Chemical compound [Ni+2].OCC([O-])=O.OCC([O-])=O OZHLXQFAHIYYDJ-UHFFFAOYSA-L 0.000 claims description 2
- OEOIWYCWCDBOPA-UHFFFAOYSA-N 6-methyl-heptanoic acid Chemical compound CC(C)CCCCC(O)=O OEOIWYCWCDBOPA-UHFFFAOYSA-N 0.000 claims description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 2
- 229910003771 Gold(I) chloride Inorganic materials 0.000 claims description 2
- VYRZVNZTWPARPF-UHFFFAOYSA-M N.[Cl-].[Rh+3] Chemical compound N.[Cl-].[Rh+3] VYRZVNZTWPARPF-UHFFFAOYSA-M 0.000 claims description 2
- 235000019445 benzyl alcohol Nutrition 0.000 claims description 2
- GAYAMOAYBXKUII-UHFFFAOYSA-L cobalt(2+);dibenzoate Chemical compound [Co+2].[O-]C(=O)C1=CC=CC=C1.[O-]C(=O)C1=CC=CC=C1 GAYAMOAYBXKUII-UHFFFAOYSA-L 0.000 claims description 2
- MPTQRFCYZCXJFQ-UHFFFAOYSA-L copper(II) chloride dihydrate Chemical compound O.O.[Cl-].[Cl-].[Cu+2] MPTQRFCYZCXJFQ-UHFFFAOYSA-L 0.000 claims description 2
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 claims description 2
- 239000012043 crude product Substances 0.000 claims description 2
- FWBOFUGDKHMVPI-UHFFFAOYSA-K dicopper;2-oxidopropane-1,2,3-tricarboxylate Chemical compound [Cu+2].[Cu+2].[O-]C(=O)CC([O-])(C([O-])=O)CC([O-])=O FWBOFUGDKHMVPI-UHFFFAOYSA-K 0.000 claims description 2
- 238000005886 esterification reaction Methods 0.000 claims description 2
- FDWREHZXQUYJFJ-UHFFFAOYSA-M gold monochloride Chemical compound [Cl-].[Au+] FDWREHZXQUYJFJ-UHFFFAOYSA-M 0.000 claims description 2
- OAKJQQAXSVQMHS-UHFFFAOYSA-N hydrazine Substances NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 claims description 2
- 229910000358 iron sulfate Inorganic materials 0.000 claims description 2
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 claims description 2
- 230000001678 irradiating effect Effects 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- RRIWRJBSCGCBID-UHFFFAOYSA-L nickel sulfate hexahydrate Chemical compound O.O.O.O.O.O.[Ni+2].[O-]S([O-])(=O)=O RRIWRJBSCGCBID-UHFFFAOYSA-L 0.000 claims description 2
- 229910000008 nickel(II) carbonate Inorganic materials 0.000 claims description 2
- ZULUUIKRFGGGTL-UHFFFAOYSA-L nickel(ii) carbonate Chemical compound [Ni+2].[O-]C([O-])=O ZULUUIKRFGGGTL-UHFFFAOYSA-L 0.000 claims description 2
- HDKCVDHYIIKWFM-UHFFFAOYSA-K octanoate;rhodium(3+) Chemical compound [Rh+3].CCCCCCCC([O-])=O.CCCCCCCC([O-])=O.CCCCCCCC([O-])=O HDKCVDHYIIKWFM-UHFFFAOYSA-K 0.000 claims description 2
- PBDBXAQKXCXZCJ-UHFFFAOYSA-L palladium(2+);2,2,2-trifluoroacetate Chemical compound [Pd+2].[O-]C(=O)C(F)(F)F.[O-]C(=O)C(F)(F)F PBDBXAQKXCXZCJ-UHFFFAOYSA-L 0.000 claims description 2
- GPNDARIEYHPYAY-UHFFFAOYSA-N palladium(ii) nitrate Chemical compound [Pd+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O GPNDARIEYHPYAY-UHFFFAOYSA-N 0.000 claims description 2
- SVOOVMQUISJERI-UHFFFAOYSA-K rhodium(3+);triacetate Chemical compound [Rh+3].CC([O-])=O.CC([O-])=O.CC([O-])=O SVOOVMQUISJERI-UHFFFAOYSA-K 0.000 claims description 2
- YBCAZPLXEGKKFM-UHFFFAOYSA-K ruthenium(iii) chloride Chemical compound [Cl-].[Cl-].[Cl-].[Ru+3] YBCAZPLXEGKKFM-UHFFFAOYSA-K 0.000 claims description 2
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- AKHNMLFCWUSKQB-UHFFFAOYSA-L sodium thiosulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=S AKHNMLFCWUSKQB-UHFFFAOYSA-L 0.000 claims description 2
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- CMTKJYPJPSONIT-UHFFFAOYSA-K trichlororuthenium;triphenylphosphane Chemical compound Cl[Ru](Cl)Cl.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 CMTKJYPJPSONIT-UHFFFAOYSA-K 0.000 claims description 2
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Abstract
本发明提供了一种单原子负载共价有机框架材料及其制备方法,以及在光解水制氢中的应用,本发明利用硫原子锚定稳定金属原子的特性,将含硫基团引入到共价有机框架孔内,含硫基团再与溶剂分子共同锚定且稳定单原子,不仅有利于单原子的稳定性,而且有益于单原子与共价有机框架之间的电荷转移,从而进一步提高单原子光催化分解水制氢的效率;本发明首次将单原子引入到共价有机框架里,制备出高催化效率,高稳定性的单原子负载共价有机光催化剂,且负载条件温和简单、普适易行、单原子负载量高,可适用于常见单原子的负载。
Description
技术领域
本发明属于材料制备及光催化技术领域,具体涉及一种单原子负载共价有机框架材料及其制备方法,以及在在光解水制氢中的应用。
背景技术
人类可持续发展所面临的两大问题分别是能源危机和环境问题。太阳能具有可再生、清洁等优点。而氢能作为一种新兴清洁能源,具有燃烧值高、储量丰富、无污染等优点,有希望替代现有化石能源,因而氢能的转换及开发成了能源领域的研究热点。目前光催化分解水技术由于能够将太阳能转化为氢能而受到广泛研究关注,利用太阳能来完成氢能的转换,是能源领域可持续发展的必然趋势。然而目前仍只能利用仅占太阳光能量的4%紫外波段光源(λ<400nm)进行分解水制氢且存在制氢效率不高的问题,因此设计和构筑廉价、高催化活性、高物化稳定性和环境友好的光催化剂,是高效利用太阳能,将光催化技术应用于实际生产的关键,决定了光解水制氢领域的发展和应用。
光解水制氢的机理是利用光催化剂受光激发产生光生电子-光生空穴,并在表面进行氧化-还原反应。光催化分解水需要满足热力学条件,理论上将一个水分子分解产生氢气和氧气需要1.23eV能量,同时由于存在着过电势,所以催化剂禁带宽度应不低于1.8eV。此外,催化剂的导带位置和价带位置应比H2/H2O电位更负,比O2/H2O电位更正,来保证有足够的还原能力和氧化能力。同时还需要满足动力学条件,H+还原为H2反应具有较高的超电势,需要选择合适的助催化剂来降低氢超电势,同时促进光生电子空穴的分离,从而实现光催化分解水。
贵金属一般显示出高的光催化活性,因此为了提高光催化剂产氢的活性,目前广泛使用的方法是在催化剂表面负载贵金属颗粒作为共催化剂,但是贵金属价格昂贵,且在催化反应过程中只有极少量的贵金属能起到催化作用,金属利用率远远低于理想水平,这无疑增加了反应成本。贵金属还易失活,这会影响光催化剂的稳定性。此外,贵金属随机分布的形貌,使得催化效果不如人意。因此,为了充分利用催化活性位点,提高金属催化剂的催化性能及分布有序程度,且维持其稳定性,成为光催化领域需要解决的问题。作为一种不同于传统纳米催化和亚纳米催化,单原子催化成为当今催化科学的最前沿课题之一。
目前,在单原子催化领域中仍存在着一些问题。当金属粒子的尺寸减小到单原子水平时,其比表面积的迅速增大会导致金属表面自由能急剧增加,容易出现团聚和催化剂失活现象。另外,金属的负载量往往比较低,这也是一个巨大的挑战。作为一类有序多孔材料,共价有机框架(COFs)材料具有结构可调控,可功能化等优点,同时还具有高的孔隙率,纳米级孔径,高温稳定性等优异性能。因此,COFs材料可作为一类理想的载体来负载单原子以有效的提高单原子的活性和稳定性。
发明内容
针对现有的光催化制氢过程中传统贵金属催化剂存在易失活,稳定性差,分布无序,负载量低,原子利用率低等问题,本发明提供了一种单原子负载共价有机框架材料及其制备方法与在光催化制氢气中的应用。
本发明采用真空加热原位还原的方法,将单原子锚定在共价有机框架孔内而制备得到单原子负载共价有机框架光催化剂,并将其应用于可见光下分解水制备氢气的反应。该体系中光催化剂具有高催化活性、高负载量、高分布有序性及高稳定性。
本发明的技术方案如下:
一种单原子负载共价有机框架材料,按如下方法制备得到:
(1)将2,5-二羟基对苯二甲酸溶解在乙醇中,以浓硫酸(98wt%)作为催化剂,在70~100℃下经酯化反应4~24h,得到2,5-二羟基对苯二甲酸二乙酯;将2,5-二羟基对苯二甲酸二乙酯分散在乙腈中,加入无水碳酸钾和2-氯乙基甲基硫醚,于50~80℃下反应12~72h,得到2,5-双(2-(甲硫基)乙氧基)对苯二甲酸二乙酯;将2,5-双(2-(甲硫基)乙氧基)对苯二甲酸二乙酯和水合肼于乙醇中回流(100℃)反应12~24h,制得酰肼类前驱体2,5-双(2-(甲硫基)乙氧基)对苯二酰肼(METPH);
(2)将醛类前驱体、步骤(1)所得酰肼类前驱体超声混合分散于溶剂中,加入酸催化剂,将反应体系放入77K液氮中冷却,冻融脱气,密封后于80~150℃下反应3~9天,之后经后处理,得到共价有机框架材料;
所述醛类前驱体、酰肼类前驱体的物质的量之比为1:1~3,优选1:1.5;
所述溶剂为纯溶剂或混合溶剂;所述溶剂的体积用量以醛类前驱体的物质的量计为1~10mL/mmol;
所述纯溶剂为均三甲苯、二氧六环、苯甲醚、1,2-邻二氯苯、二甲基乙酰胺、甲基吡咯烷酮、正丁醇、苯甲醇或乙醇;
所述混合溶剂为溶剂A/溶剂B体积比1:1~9的混合,所述溶剂A/溶剂B为均三甲苯/二氧六环、邻二氯苯/二氧六环、苯甲醚/二氧六环、邻二氯苯/正丁醇、苯甲醚/正丁醇、均三甲苯/正丁醇、甲基吡咯烷酮/均三甲苯或二甲基乙酰胺/邻二氯苯;“溶剂A”、“溶剂B”没有特殊的含义,标记为“A”、“B”只是用于区分不同种类的溶剂;
所述酸催化剂为3~9M醋酸水溶液,酸催化剂与溶剂的体积比为0.1~1:1;
所述后处理的方法为:反应结束后,将反应液过滤,滤出的粗产物分别于N,N-二甲基甲酰胺、四氢呋喃、丙酮中进行洗涤和离心过滤3~5遍,避光风干后进行避光常温真空干燥,得到共价有机框架材料;
所述醛类前驱体选自如下一种或几种:
(3)将金属前驱体溶于混合溶剂,再将步骤(2)所得共价有机框架材料浸泡于该溶液中12~72h,之后过滤,清洗(用上述混合溶剂),再将清洗后的共价有机框架材料浸泡在还原剂中,将体系放入77K液氮中冷却,冻融脱气,密封后在25~100℃下反应1~12h,之后经后处理,得到单原子负载共价有机框架材料;
所述金属前驱体为:六水合氯铂酸、氯铂酸钾、六氰基铂(IV)酸钾、硝酸钯、新戊酸钯、三氟乙酸钯、四氯金酸、氯金酸钾、氯(二甲基硫化)金(I)、异辛酸钴、苯甲酸钴、硫酸镍(II)六水合物、碳酸镍、羟乙酸镍、三氯化钌、四丙基高钌酸铵、三苯基膦氯化钌、辛酸铑、醋酸铑、氯铑酸铵、氯化锌、七水合硫酸锌、对甲苯磺酸锌、无水硫酸铁、福美铁、硝酸铁(III)、氯化铱、羰基铱、十二羰基四铱、无水硫酸铜(II)、氯化铜(II)二水合物、柠檬酸铜中的一种或几种;
相应的,所得单原子负载共价有机框架材料中的单原子为:铂(Pt)、钯(Pd)、金(Au)、钴(Co)、镍(Ni)、钌(Ru)、铑(Rh)、锌(Zn)、铁(Fe)、铱(Ir)、铜(Cu)中的一种或几种;
所述共价有机框架材料、金属前驱体的质量比为0.1~10:1;
所述混合溶剂为丙酮、四氢呋喃、乙醇、甲醇、水、二氧六环、二氯甲烷中任意两种组成的混合溶剂,且两种溶剂体积比为0.1~10:1;所述混合溶剂的体积用量以金属前驱体的质量计为0.1~10mL/mg;
所述还原剂为乙醇、甲醇、苯酚、5~30wt%硼氢化钠水溶液、5~30wt%抗坏血酸水溶液、5~30wt%硫代硫酸钠水溶液中一种或几种;所述还原剂的体积用量以共价有机框架的质量计为0.01~10mL/mg;
所述后处理的方法为:反应结束后,将反应液过滤,滤出的固体产物用甲醇、乙醇、丙酮、四氢呋喃和二氯甲烷进行离心和过滤,最后避光下常温风干,得到单原子负载共价有机框架材料。
本发明制备的单原子负载共价有机框架材料可应用于光解水制氢气反应。
具体的,所述应用的方法为:
在光解水反应器中,将单原子负载共价有机框架材料分散在甲醇/水溶液中,加入牺牲剂,加入磁子搅拌,抽真空,用300W氙灯照射,在温度10~30℃,0.1~10W/cm2的光功率密度下反应得到氢气;
所述甲醇/水溶液的体积用量以单原子负载共价有机框架材料的质量计为0.01~10mL/mg;
所述的牺牲剂、甲醇、水的体积比为1:0~4:9~5;
所述牺牲剂为甲醇、三乙醇胺、抗坏血酸中的一种;
所述搅拌转速为50~3000rpm;
所述抽真空到系统压强为0.1~20kPa。
本发明单原子负载共价有机框架光催化剂的制备原理为,以孔内具有功能化基团的共价有机框架为载体,利用溶液浸渍结合加热醇原位还原的方法实现单原子负载共价有机光催化剂。该方法利用硫原子锚定稳定金属原子的特性,将含硫基团引入到共价有机框架孔内,含硫基团再与溶剂分子共同锚定且稳定单原子,不仅有利于单原子的稳定性,而且有益于单原子与共价有机框架之间的电荷转移,从而进一步提高单原子光催化分解水制氢的效率。
与现有技术相比,本发明具有以下有益的技术效果:
本发明结合功能化的共价有机框架(COFs),通过在功能化的COFs孔内负载单原子,使得单原子的超高催化活性和COFs耐溶剂的优异特性结合起来,制备出一种用于光催化制氢气的单原子负载共价有机框架催化剂,不仅解决了传统光解水催化剂活性低、负载量低、贵金属原子利用率低的问题,且相比于传统贵金属催化剂,所制备的单原子负载共价有机框架材料催化剂具有高负载量,高原子利用率、高活性和稳定性等优点。此外,目前文献及专利中尚无单原子负载共价有机框架催化剂的报道。
本发明的显著优点在于:
(1)共价有机框架是一类具有结构可调控,可功能化等优点,同时还具有高的孔隙率,纳米级孔径,高温稳定性等优异性能的有序多孔材料。本发明首次将单原子引入到共价有机框架里,制备出高催化效率,高稳定性的单原子负载共价有机光催化剂。
(2)本发明的光催化剂,其单原子负载条件温和简单、普适易行、单原子负载量高,可适用于常见单原子的负载。不仅有利于大规模的推广,还有利于负载各种单原子以适应各种常见的反应,具有广阔的前景。
附图说明
图1为实施例2中制备的共价有机框架材料S-TFPT的实验及模拟粉末衍射图。
图2为实施例3中制备的单原子负载共价有机框架材料PtSA@S-TFPT的球差电镜图。
图3为实施例4中单原子负载共价有机框架材料PtSA@S-TFPT的光催化分解水制氢气实验结果。
图4为单原子负载共价有机框架材料PtSA@S-TFPT的光催化分解水制氢气的模型图。
具体实施方式
下面通过具体实施例对本发明作进一步的描述,但本发明的保护范围并不仅限于此。
实施例1:酰肼类前驱体METPH的制备
将5g 2,5-二羟基对苯二甲酸溶解在50mL乙醇中,以5mL浓硫酸作为催化剂,在80℃下反应24h后,将反应体系冷却至室温过滤,并将所得固体抽滤并用乙醇和去离子水清洗,得到2,5-二羟基对苯二甲酸二乙酯。将2.5g 2,5-二羟基对苯二甲酸二乙酯分散在30mL乙腈中,加入6g碳酸钾和3.3g 2-氯乙基甲基硫醚,在80℃下反应48h后,将反应体系冷却至室温后倒入100mL去离子水中,并用乙酸乙酯(3×100mL)萃取三次,合并所得乙酸乙酯相干燥旋蒸得到中间产物2,5-双(2-(甲硫基)乙氧基)对苯二甲酸二乙酯。将2g上述所得中间产物和2mL水合肼于40mL乙醇中回流反应12h后,将反应体系冷却至室温过滤,并将所得固体抽滤并用乙醇和去离子水清洗,得到酰肼类前驱体METPH。
实施例2:共价有机框架材料S-TFPT的制备
将0.1mmol的1,3,5-三-(4-甲酰基苯基)三嗪、0.15mmol的METPH和3mL的三甲苯/二氧六环(体积比3:2)混合,超声分散均匀后,加入10mL耐压史莱克管中,再加入0.3mL的6M乙酸,放入77K液氮中冷却,冻融脱气三次后在烘箱中于120℃下反应7天。反应结束再对产物进行分离和纯化,得到共价有机框架材料S-TFPT。
按照上述合成方法,将1,3,5-三-(4-甲酰基苯基)三嗪替换成1,3,5-三-(4-甲酰基苯基)苯或者1,3,5-三羟基均苯三甲醛或者一定比例的混合醛等醛类前驱体,与METPH组装可以得到其他共价有机框架材料。
实施例3:单原子负载共价有机框架材料PtSA@S-TFPT的制备
将33mg的六水合氯铂酸超声溶于8mL 25vt%甲醇/水溶液,再将60mg上述共价有机框架材料浸泡于该溶液中,浸泡3天饱和后,经过滤洗涤后,将所得产物转移至10mL耐压史莱克管中,加入3mL无水乙醇,将反应体系放入77K液氮中冷却,冻融脱气三次后在60℃下反应1.5h,以浸渍原位反应,再对产物进行分离和纯化,得到单原子铂(Pt)负载共价有机框架材料PtSA@S-TFPT。
将共价有机框架材料S-TFPT替换成依实施例2方法得到的其他共价有机框架材料,并以上述方法负载单原子铂(Pt)可以得到单原子铂(Pt)负载的其他共价有机框架材料。
将六水合氯铂酸替换成其它金属前驱体,以上述方法负载其它单原子,得到不同的单原子负载共价有机框架材料。
实施例4:单原子负载共价有机框架材料用于光解水制氢
将20mg上述单原子铂(Pt)负载共价有机框架材料加入至35mL去离子水中,再加入5mL甲醇,超声分散1h。将分散好单原子负载共价有机框架材料的混合溶液加入光催化反应系统(Labsolar 6A;北京泊菲莱科技有限公司)中,加入5mL三乙醇胺(TEOA)作为牺牲剂,加入磁子于500rpm下搅拌,使用300W氙灯于1W/cm2的光功率密度下用波长>420nm的光进行光照。产物氢气由气相色谱系统(GC2002;上海科创色谱仪器有限公司)检测。测试量子产率时,按照相同方法,分别使用420nm、450nm、520nm的滤光片提供单一波长的光,使用光辐照计(LP-100长春新产业光电技术有限公司)将光功率密度测试调至为100mW/cm2,进行测试。按照以下公式进行计算表观量子产率(AQE):
(1)单位时间氙灯产生的光子数为:
式中W——光功率;h——普朗克常数;c——光速;λ——光波长;υ——光频率;n——单位时间内产生的光子数。
(2)单位时间内产氢的表观量子产率为:
式中AQE——单位时间内产氢的表观量子产率;——单位时间内产生的氢气的量;N0——阿伏伽德罗常数;n——单位时间内产生的光子数。
(3)光功率和光功率密度换算为:
W=I×A
式中W——光功率;I——光功率密度;A——有效光辐照面积。
结果为:产氢速率为11400μmol/(g·h),稳定性优异,循环3次(3×3h),其性能无明显衰减。在420nm波长下,光量子产率为4.6%。
对比例:(CN 111569942A)
共价三嗪有机骨架的制备,具体步骤为:在0℃且搅拌条件下,将12mL三氟甲磺酸加入到30mL三氯甲烷中形成混合溶液,将溶解有4.26g对苯二腈的200mL三氯甲烷溶液在氮气氛围下逐滴加入混合溶液中,搅拌2h,更换油浴加热升温至40℃,继续搅拌48h;用pH=8~9的氨水水溶液搅拌2h,水洗至中性,冷冻干燥;将冷冻干燥的样品与ZnCl2以摩尔比为1:0.8研磨均匀,在400℃和氩气条件下煅烧10min,然后分别用0.5mol/L的盐酸水溶液和去离子水洗涤数次,冷冻干燥,即得共价三嗪有机骨架,记为CTF-1。
CTF-COOH的制备:将0.2g预先合成的共价三嗪有机骨架分散于50mL乙醇-水(V/V=1:1)的混合溶液中,超声搅拌15min至其分散均匀,然后加热升温至120℃,并在搅拌条件下加入0.5g氢氧化钠,保持加热温度回流反应5h;然后冷却至室温,分别用0.5mol/L盐酸溶液和去离子水洗涤、离心至离子浓度小于100ppm,冷冻干燥得CTF-COOH。
Pt-CTF-COOH的制备:称取0.1gCTF-COOH分散于含15mL去离子水和5mL甲醇的混合溶液中并超声均匀,在搅拌条件下加入129μL40 mmol/L的氯铂酸水溶液,在氮气氛围下可见光原位还原4h,完成后离心,用甲醇洗涤数次,所得样品在室温下干燥,即得到表面限域单分散Pt纳米颗粒的共价三嗪有机骨架Pt-CTF-COOH复合光催化剂。
将制备的Pt-CTF-COOH用作光催化剂,在可见光激发下实现水分解制氢的应用,其具体是称取20mg Pt-CTF-COOH复合光催化剂,分散于80mL含有8mL三乙醇胺的水溶液中,搅拌均匀,在真空条件下开启光源进行光催化反应,产物使用气相色谱检测。实验用光源为300W氙灯,使用滤光片以保证入射光为可见光(420nm<λ<800nm),其产氢速率为4800μmol/(g·h)。
相比于对比例,本发明中单原子负载共价有机框架材料催化剂在光解水产氢性能与稳定性等方面都大大优于同类贵金属颗粒负载光催化剂。
图1为实施例2中制备的共价有机框架材料S-TFPT的试验和模拟粉末衍射图,从图中可以看出S-TFPT采取二维层间AA堆积模式,并在2.29°,4.67°,6.14°,7.96°,26.32°具有布拉格峰,分别对应(100),(200),(210),(220)和(001)晶面。
图2为实施例3中制备的单原子铂(Pt)负载共价有机框架材料PTSA@S-TFPT的球差电镜图,从球差电镜图中可以看出,所制备的单原子负载共价有机框架材料负载的单原子不仅负载量高,且在大范围上看也无颗粒。
图3为实施例4中单原子铂(Pt)负载共价有机框架材料的光催化分解水制氢气实验结果,从图中可以看出,所制备的单原子铂(Pt)负载共价有机框架材料具有优异的光解水产氢活性,氢气产生速率高达11.4mmol/(g·h);此外该催化剂稳定性好,循环3次,其性能无明显衰减。
以上详细描述了本发明的较佳实施例。应当理解,本领域的普通技术人员无需创造性劳动就可以根据本发明的构思做出诸多修改和变化。凡本技术领域中技术人员依本发明的构思在现有技术的基础上通过逻辑分析、推理或者有限的实验可以得到的实验与技术方案,皆应在由权利要求书所确定的保护范围内。
Claims (9)
1.一种单原子负载共价有机框架材料,其特征在于,按如下方法制备得到:
(1)将2,5-二羟基对苯二甲酸溶解在乙醇中,以浓硫酸作为催化剂,在70~100℃下经酯化反应4~24h,得到2,5-二羟基对苯二甲酸二乙酯;将2,5-二羟基对苯二甲酸二乙酯分散在乙腈中,加入无水碳酸钾和2-氯乙基甲基硫醚,于50~80℃下反应12~72h,得到2,5-双(2-(甲硫基)乙氧基)对苯二甲酸二乙酯;将2,5-双(2-(甲硫基)乙氧基)对苯二甲酸二乙酯和水合肼于乙醇中回流反应12~24h,制得酰肼类前驱体2,5-双(2-(甲硫基)乙氧基)对苯二酰肼(METPH);
(2)将醛类前驱体、步骤(1)所得酰肼类前驱体超声混合分散于溶剂中,加入酸催化剂,将反应体系放入77K液氮中冷却,冻融脱气,密封后于80~150℃下反应3~9天,之后经后处理,得到共价有机框架材料;
所述醛类前驱体、酰肼类前驱体的物质的量之比为1:1~3;
所述酸催化剂为3~9M醋酸水溶液;
所述醛类前驱体选自如下一种或几种:
(3)将金属前驱体溶于混合溶剂,再将步骤(2)所得共价有机框架材料浸泡于该溶液中12~72h,之后过滤,清洗,再将清洗后的共价有机框架材料浸泡在还原剂中,将体系放入77K液氮中冷却,冻融脱气,密封后在25~100℃下反应1~12h,之后经后处理,得到单原子负载共价有机框架材料;
所述金属前驱体为:六水合氯铂酸、氯铂酸钾、六氰基铂(IV)酸钾、硝酸钯、新戊酸钯、三氟乙酸钯、四氯金酸、氯金酸钾、氯(二甲基硫化)金(I)、异辛酸钴、苯甲酸钴、硫酸镍(II)六水合物、碳酸镍、羟乙酸镍、三氯化钌、四丙基高钌酸铵、三苯基膦氯化钌、辛酸铑、醋酸铑、氯铑酸铵、氯化锌、七水合硫酸锌、对甲苯磺酸锌、无水硫酸铁、福美铁、硝酸铁(III)、氯化铱、羰基铱、十二羰基四铱、无水硫酸铜(II)、氯化铜(II)二水合物、柠檬酸铜中的一种或几种;
所述共价有机框架材料、金属前驱体的质量比为0.1~10:1。
2.如权利要求1所述单原子负载共价有机框架材料,其特征在于,步骤(2)中,所述溶剂为纯溶剂或混合溶剂;所述溶剂的体积用量以醛类前驱体的物质的量计为1~10mL/mmol;所述纯溶剂为均三甲苯、二氧六环、苯甲醚、1,2-邻二氯苯、二甲基乙酰胺、甲基吡咯烷酮、正丁醇、苯甲醇或乙醇;所述混合溶剂为溶剂A/溶剂B体积比1:1~9的混合,所述溶剂A/溶剂B为均三甲苯/二氧六环、邻二氯苯/二氧六环、苯甲醚/二氧六环、邻二氯苯/正丁醇、苯甲醚/正丁醇、均三甲苯/正丁醇、甲基吡咯烷酮/均三甲苯或二甲基乙酰胺/邻二氯苯。
3.如权利要求1所述单原子负载共价有机框架材料,其特征在于,步骤(2)中,所述酸催化剂与溶剂的体积比为0.1~1:1。
4.如权利要求1所述单原子负载共价有机框架材料,其特征在于,步骤(2)中,所述后处理的方法为:反应结束后,将反应液过滤,滤出的粗产物分别于N,N-二甲基甲酰胺、四氢呋喃、丙酮中进行洗涤和离心过滤3~5遍,避光风干后进行避光常温真空干燥,得到共价有机框架材料。
5.如权利要求1所述单原子负载共价有机框架材料,其特征在于,步骤(3)中,所述混合溶剂为丙酮、四氢呋喃、乙醇、甲醇、水、二氧六环、二氯甲烷中任意两种组成的混合溶剂,且两种溶剂体积比为0.1~10:1;所述混合溶剂的体积用量以金属前驱体的质量计为0.1~10mL/mg。
6.如权利要求1所述单原子负载共价有机框架材料,其特征在于,步骤(3)中,所述还原剂为乙醇、甲醇、苯酚、5~30wt%硼氢化钠水溶液、5~30wt%抗坏血酸水溶液、5~30wt%硫代硫酸钠水溶液中一种或几种;所述还原剂的体积用量以共价有机框架的质量计为0.01~10mL/mg。
7.如权利要求1所述单原子负载共价有机框架材料,其特征在于,步骤(3)中,所述后处理的方法为:反应结束后,将反应液过滤,滤出的固体产物用甲醇、乙醇、丙酮、四氢呋喃和二氯甲烷进行离心和过滤,最后避光下常温风干,得到单原子负载共价有机框架材料。
8.如权利要求1所述单原子负载共价有机框架材料在光解水制氢气反应中的应用。
9.如权利要求8所述的应用,其特征在于,所述应用的方法为:
在光解水反应器中,将单原子负载共价有机框架材料分散在甲醇/水溶液中,加入牺牲剂,加入磁子搅拌,抽真空,用300W氙灯照射,在温度10~30℃,0.1~10W/cm2的光功率密度下反应得到氢气;
所述甲醇/水溶液的体积用量以单原子负载共价有机框架材料的质量计为0.01~10mL/mg;
所述的牺牲剂、甲醇、水的体积比为1:0~4:9~5;
所述牺牲剂为甲醇、三乙醇胺、抗坏血酸中的一种;
所述搅拌转速为50~3000rpm;
所述抽真空到系统压强为0.1~20kPa。
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