不同晶体形貌NH_2-MIL-125(Ti)的制备及光催化性能
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摘要
以2-氨基对苯二甲酸(H_2ATA)和钛酸四异丙酯〔Ti(C_3H_7O)_4〕为原料,采用溶剂热法合成了NH_2-MIL-125(Ti)晶体,通过调变溶剂N,N-二甲基甲酰胺(DMF)和无水甲醇的体积比,NH_2-MIL-125(Ti)晶体呈现出圆片形、十面体和八面体形貌。采用XRD、SEM、FTIR和BET等手段对不同形貌的NH_2-MIL-125(Ti)晶体进行了物性分析,并将其用于可见光光催化环己烷的氧化反应,探究了催化性能与晶面之间的构效关系。结果表明,环己烷选择性氧化生成环己醇和环己酮目标产物主要反应发生在NH_2-MIL-125(Ti)晶体的{110}晶面族,而{101}晶面族可以进一步氧化环己醇和环己酮产生CO和CO_2。
NH_2-MIL-125(Ti) crystals were prepared using 2-aminoterephthalic acid(H_2 ATA) and tetraisopropyl titanate〔Ti(C_3 H_7 O)_4〕 as raw materials by a solvothermal method. By varying the volume ratio of N,N-dimethylformamide(DMF) to methanol(MeOH) in the synthesis system, NH_2-MIL-125(Ti)crystals exhibited circular plate, decahedral or octahedral morphology. XRD, SEM, FTIR and BET characterization techniques were used to study the physical properties of NH_2-MIL-125(Ti) crystals with different morphologies. Then these crystals were used in the photocatalytic oxidation of cyclohexane under visible light irradiation. The structure-activity relationship between catalytic performance and crystal plane was explored. Results showed that the main reaction of selective oxidation of cyclohexane to target products cyclohexanol and cyclohexanone occurs in the {110} crystal face family of NH_2-MIL-125(Ti)crystals, whereas the {101} crystal face family is mainly to further oxidize cyclohexanol and cyclohexanone into CO and CO_2.
NH_2-MIL-125(Ti) crystals were prepared using 2-aminoterephthalic acid(H_2 ATA) and tetraisopropyl titanate〔Ti(C_3 H_7 O)_4〕 as raw materials by a solvothermal method. By varying the volume ratio of N,N-dimethylformamide(DMF) to methanol(MeOH) in the synthesis system, NH_2-MIL-125(Ti)crystals exhibited circular plate, decahedral or octahedral morphology. XRD, SEM, FTIR and BET characterization techniques were used to study the physical properties of NH_2-MIL-125(Ti) crystals with different morphologies. Then these crystals were used in the photocatalytic oxidation of cyclohexane under visible light irradiation. The structure-activity relationship between catalytic performance and crystal plane was explored. Results showed that the main reaction of selective oxidation of cyclohexane to target products cyclohexanol and cyclohexanone occurs in the {110} crystal face family of NH_2-MIL-125(Ti)crystals, whereas the {101} crystal face family is mainly to further oxidize cyclohexanol and cyclohexanone into CO and CO_2.
引文
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[2]Shen L J,Wu W M,Liang R W,et al.Highly dispersed palladium nanoparticles anchored on UiO-66(NH2)metal-organic framework as a reusable and dual functional visible-light-driven photocatalyst[J].Nanoscale,2013,5(19):9374-9382.
[3]Shi L,Wang T,Zhang H,et al.An amine-functionalized iron(Ⅲ)metal-organic framework as efficient visible-light photocatalyst for Cr(Ⅵ)reduction[J].Advanced Science,2015,2(3):1500006.
[4]Ferrando-Soria J,Khajavi H,Serra-Crespo,P,et al.Highly selective chemical sensing in a luminescent nanoporous magnet[J].Advanced Materials,2012,24(41):5625-5629.
[5]Kang Z X,Xue M,Fan L L,et al.Highly selective sieving of small gas molecules by using an ultra-microporous metal-organic framework membrane[J].Energy&Environmental Science,2014,7(12):4053-4060.
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[8]Lu C J,Ben T,Xu S X,et al.Electrochemical synthesis of a microporous conductive polymer based on a metal-organic framework thin film[J].Angewandte Chemie-international Edition,2014,53(25):6454-6458.
[9]Talin A A,Centrone A,Ford A C,et al.Tunable electrical conductivity in metal-organic framework thin-film devices[J].Science,2014,343(6166):66-69.
[10]Yoon S M,Warren S C,Grzybowski B A.Storage of electrical information in metal-organic-framework memristors[J].Angewandte Chemie-international Edition,2014,53(17):4437-4441.
[11]Zeng M H,Yin Z,Tan Y X,et al.Nanoporous Cobalt(Ⅱ)MOFexhibiting four magnetic ground states and changes in gas sorption upon post-synthetic modification[J].Journal of the American Chemical Society,2014,136(12):4680-4688.
[12]Bi Y,Ouyang S,Umezawa N,et al.Facet effect of single-crystalline Ag3PO4 sub-microcrystals on photocatalytic properties[J].Journal of the American Chemical Society,2011,133(17):6490-6492.
[13]He Z,Jiang L,Da W,et al.Simultaneous oxidation of p-chlorophenol and reduction of Cr(Ⅵ)on fluorinated anatase TiO2 nanosheets with dominant{001}facets under visible irradiation}[J].Industrial&Engineering Chemistry Research,2015,54(3):808-818.
[14]Hu S,Liu M,Guo X,et al.Effect of titanium ester on synthesizing NH2-MIL-125(Ti):morphology changes from circular plate to octahedron and rhombic dodecahedron[J].Journal of Solid State Chemistry,2018,262:237-243.
[15]Zlotea C,Phanon D,Mazaj M,et al.Effect of NH2 and CF3functionalization on the hydrogen sorption properties of MOFs[J].Dalton Translations,2011,40(18):4879-4881.
[16]Fu Y,Sun D,Chen Y,et al.An amine-functionalized titanium metal-organic framework photocatalyst with visible-light-induced activity for CO2 reduction[J].Angewandte Chemie,2012,51(14):3364-3367.
[17]Yang J M,Liu Q,Sn W Y,et al.Shape and size control and gas adsorption of Ni(Ⅱ)-doped MOF-5 nano/microcrystals[J].Microporous Mesoporous Mater,2014,190(15):26-31.
[18]Liang R W,Shen L J,Jing F F,et al.NH2-mediated indium metalorganic framework as a novel visible-light-driven photocatalyst for reduction of the aqueous Cr(Ⅵ)[J].Applied Catalysis B:Environmental,2015,162:245-251.
[19]Shen L J,Ling S J,Wu W M,et al.Multifunctional NH2-mediated zirconium metal-organic framework as an efficient visible-lightdriven photocatalyst for selective oxidation of alcohols and reduction of aqueous Cr(Ⅵ)[J].Dalton Transactions,2013,42:13649-13657.
[20]Zhu W,Liu P J,Xiao S N,et al.Microwave-assisted synthesis of Agdoped MOFs-like organotitanium polymer with high activity in visiblelight driven photocatalytic NO oxidization[J].Applied Catalysis B:Environmental,2015,172/173:46-51.
[21]WU J C S,Cheng Y T.In situ FTIR study of photocatalytic NOreaction on photocatalysts under UV irradiation[J].Journal of Catalysis,2006,237(2):393-404.
[22]Yang Z W,Xu X Q,Liang X X,et al.MIL-53(Fe)-graphene nanocomposites:Efficient visible-light photocatalysts for the selective oxidation of alcohols[J].Applied Catalysis B:Environmental,2016,198:112-123.
[23]Xu Jing(许静).Preparation of NH2-MIL-125 membrane and study of its separation performance[D].Dalian:Dalian University of Technology(大连理工大学),2015.
[24]Fu Y H,Sun D R,Chen Y J,et al.An amine-functionalized titanium metal-organic framework photocatalyst with visible-light-induced activity for CO2 reduction[J].Angewandte Chemie International Edition,2012,51(14):3364-3367.