CN110302840B - 一种MnO2/Cu-Al-BTC三元金属有机骨架材料的制备方法及应用 - Google Patents
一种MnO2/Cu-Al-BTC三元金属有机骨架材料的制备方法及应用 Download PDFInfo
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- 239000000463 material Substances 0.000 title claims abstract description 52
- 239000012621 metal-organic framework Substances 0.000 title claims abstract description 21
- 238000000034 method Methods 0.000 title claims abstract description 17
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Inorganic materials O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 claims abstract description 20
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims abstract description 18
- 238000002360 preparation method Methods 0.000 claims abstract description 17
- 229910017767 Cu—Al Inorganic materials 0.000 claims abstract description 16
- 239000002243 precursor Substances 0.000 claims abstract description 16
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000011259 mixed solution Substances 0.000 claims abstract description 12
- 239000000411 inducer Substances 0.000 claims abstract description 7
- 239000005711 Benzoic acid Substances 0.000 claims abstract description 6
- 235000010233 benzoic acid Nutrition 0.000 claims abstract description 6
- PKPQWDSIINFZNV-UHFFFAOYSA-L dichlorocopper;ethane-1,2-diamine Chemical compound [Cl-].[Cl-].[Cu+2].NCCN PKPQWDSIINFZNV-UHFFFAOYSA-L 0.000 claims abstract description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims abstract description 3
- 239000000243 solution Substances 0.000 claims description 22
- 239000007787 solid Substances 0.000 claims description 19
- QMKYBPDZANOJGF-UHFFFAOYSA-N benzene-1,3,5-tricarboxylic acid Chemical compound OC(=O)C1=CC(C(O)=O)=CC(C(O)=O)=C1 QMKYBPDZANOJGF-UHFFFAOYSA-N 0.000 claims description 18
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 13
- 238000006243 chemical reaction Methods 0.000 claims description 12
- 238000003756 stirring Methods 0.000 claims description 10
- 229910021642 ultra pure water Inorganic materials 0.000 claims description 10
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- 239000012697 Mn precursor Substances 0.000 claims description 7
- 150000002500 ions Chemical class 0.000 claims description 6
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- 229910021380 Manganese Chloride Inorganic materials 0.000 claims description 5
- GLFNIEUTAYBVOC-UHFFFAOYSA-L Manganese chloride Chemical compound Cl[Mn]Cl GLFNIEUTAYBVOC-UHFFFAOYSA-L 0.000 claims description 5
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- 235000002867 manganese chloride Nutrition 0.000 claims description 5
- 239000011565 manganese chloride Substances 0.000 claims description 5
- CNFDGXZLMLFIJV-UHFFFAOYSA-L manganese(II) chloride tetrahydrate Chemical compound O.O.O.O.[Cl-].[Cl-].[Mn+2] CNFDGXZLMLFIJV-UHFFFAOYSA-L 0.000 claims description 5
- HPEUJPJOZXNMSJ-UHFFFAOYSA-N Methyl stearate Chemical compound CCCCCCCCCCCCCCCCCC(=O)OC HPEUJPJOZXNMSJ-UHFFFAOYSA-N 0.000 claims description 4
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- 229940051841 polyoxyethylene ether Drugs 0.000 claims description 4
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- 239000000843 powder Substances 0.000 claims description 3
- DUIOKRXOKLLURE-UHFFFAOYSA-N 2-octylphenol Chemical compound CCCCCCCCC1=CC=CC=C1O DUIOKRXOKLLURE-UHFFFAOYSA-N 0.000 claims description 2
- RZXLPPRPEOUENN-UHFFFAOYSA-N Chlorfenson Chemical compound C1=CC(Cl)=CC=C1OS(=O)(=O)C1=CC=C(Cl)C=C1 RZXLPPRPEOUENN-UHFFFAOYSA-N 0.000 claims description 2
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 claims description 2
- 150000001879 copper Chemical class 0.000 claims description 2
- CAMHHLOGFDZBBG-UHFFFAOYSA-N epoxidized methyl oleate Natural products CCCCCCCCC1OC1CCCCCCCC(=O)OC CAMHHLOGFDZBBG-UHFFFAOYSA-N 0.000 claims description 2
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- 239000008204 material by function Substances 0.000 abstract 1
- 239000000126 substance Substances 0.000 abstract 1
- 230000001965 increasing effect Effects 0.000 description 25
- MWUXSHHQAYIFBG-UHFFFAOYSA-N Nitric oxide Chemical compound O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 18
- 239000002994 raw material Substances 0.000 description 11
- 229910052782 aluminium Inorganic materials 0.000 description 8
- 239000000203 mixture Substances 0.000 description 8
- 239000010949 copper Substances 0.000 description 7
- 230000015572 biosynthetic process Effects 0.000 description 6
- 230000003197 catalytic effect Effects 0.000 description 6
- 229910052802 copper Inorganic materials 0.000 description 6
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- 238000011160 research Methods 0.000 description 3
- 239000013148 Cu-BTC MOF Substances 0.000 description 2
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- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 2
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- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 229910021592 Copper(II) chloride Inorganic materials 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
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- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
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- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 description 1
- BXZCTOIDCRWONQ-UHFFFAOYSA-N copper;ethane-1,2-diamine Chemical compound [Cu+2].NCCN BXZCTOIDCRWONQ-UHFFFAOYSA-N 0.000 description 1
- 230000005595 deprotonation Effects 0.000 description 1
- 238000010537 deprotonation reaction Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
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- 230000002708 enhancing effect Effects 0.000 description 1
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- 238000005470 impregnation Methods 0.000 description 1
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- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
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- 230000009467 reduction Effects 0.000 description 1
- 238000006722 reduction reaction Methods 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 238000001757 thermogravimetry curve Methods 0.000 description 1
- NOSIKKRVQUQXEJ-UHFFFAOYSA-H tricopper;benzene-1,3,5-tricarboxylate Chemical compound [Cu+2].[Cu+2].[Cu+2].[O-]C(=O)C1=CC(C([O-])=O)=CC(C([O-])=O)=C1.[O-]C(=O)C1=CC(C([O-])=O)=CC(C([O-])=O)=C1 NOSIKKRVQUQXEJ-UHFFFAOYSA-H 0.000 description 1
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Abstract
本发明属于新型功能性材料设计与制备技术领域,提供了一种MnO2/Cu‑Al‑BTC三元金属有机骨架材料的制备方法及应用。本发明以微波辅助加热‑浸渍联合法为合成方法,选择苯甲酸与乙酸混合液作为稳定剂,以氯化二羟基‑双四甲基亚乙基二胺铜(II)、(十八烷‑9‑烯基乙酰乙酸根合‑O1’,O3)二丙烷‑2‑醇合铝作为金属盐合成出理化性能优异的Cu‑Al前驱体材料。之后,选择FMES和OP‑6作为分子诱导剂,诱导MnO2进入Cu‑Al前驱体材料的骨架结构内部,制备出具有三元金属活性位点的MnO2/Cu‑Al‑BTC催化剂。该材料取得了90%‑96%的脱硝效率,且可保持结构稳定直到340℃。
Description
技术领域
本发明涉及一种新型MnO2/Cu-Al-BTC三元金属有机骨架材料的制备方法及其在CO选择性催化还原反应脱硝(CO-SCR)方面的应用,属于新型功能性材料设计与制备技术领域。
背景技术
氮氧化物(NOx)排放会形成诸如酸雨、光化学烟雾等环境污染事件,对人体健康和生态环境产生严重危害。由于目前我国NOx的排放尚未完全得到控制,因此对于NOx的污染控制及减排是当前我国环境领域要解决的重点问题。在诸多的NOx脱除方法中,选择性催化还原法(Selective Catalytic Reduction,SCR) 是当前使用范围最广并且效果最好的脱硝技术。在SCR技术中,常使用NH3,CO, H2,碳氢化合物等作为还原剂,其中,CO-SCR技术由于具有催化剂寿命长,能够同时去除CO,NOx两种污染物的优点而成为SCR技术的研究趋势。对于 CO-SCR技术而言,催化剂的开发与选择是决定该反应脱硝性能的关键。在催化剂方面,SCR催化剂主要包括贵金属催化剂、分子筛催化剂和金属氧化物催化剂等。但现有的催化剂存在着价格昂贵、选择性差、稳定性差等问题,因此目前CO-SCR技术所要解决的关键科学问题就是开发出一种具有较好的脱硝效率、选择性强、热稳定性高,同时价格低廉的新型催化剂。
近年来,新兴的MOFs系列材料被视为一种较为理想的SCR催化剂。MOFs 材料主要有如下优点:巨大的比表面积能够为反应提供反应场所;不饱和金属位点能够对反应气体进行吸附,并催化反应;同时可调控的拓扑结构能够增强对气体的选择性;具有优异的热稳定性,这些特征为MOFs材料催化CO-SCR 反应奠定基础。在MOFs材料中,不同的金属中心离子在提高脱硝效率、增强稳定性、降低反应温度等方面起着不同的作用。如何对不同功能的金属离子进行选择和组合,使其能够协同催化CO-SCR反应,提高催化剂性能,是当前MOFs材料脱硝领域的研究重点。
Jiang等人的研究已表明Cu-BTC具有一定的SCR活性,同时,三价金属阳离子如Al3+离子可以在材料的晶格内替换掉部分Cu2+,从而增加材料的电荷密度,进一步促进金属活性位点的产生和均匀分散。因此,首先选择Cu、Al作为金属中心离子,合成出Cu-Al前驱体材料是可行的。而锰基氧化物催化剂已被证明能够有效降低催化剂的起活温度,因此含有Cu、Al、Mn三元金属的MOFs 材料可能是一种具有较好的低温活性和脱硝效率的新型催化剂。然而目前,合成MOFs材料存在以下问题:常用的水热法存在能耗高、耗时长的问题;已报道的Cu-BTC MOFs经常使用硝酸盐为金属离子的来源,但其存在产率不高、金属活性位点分散性差、催化效率低等问题;均匀、稳定、高催化活性的 MnO2/Cu-Al-BTC三元金属有机骨架材料的合成及其CO-SCR应用尚未见报导。
发明内容
本发明以微波辅助加热-浸渍联合法为合成方法,以使用特定的分子诱导剂诱导MnO2进入MOFs骨架结构内部为设计策略,提出一种新型的 MnO2/Cu-Al-BTC三元金属有机骨架材料的设计及制备方法,并将其应用于催化 CO-SCR脱硝技术中,该材料具有均匀、稳定、高催化活性的特点,。
本发明首先采用微波辅助加热法合成Cu-Al前驱体材料,有效的解决了常用的水热法存在的能耗高、耗时长的问题。在合成过程中首次选择了特定的酸性溶液作为稳定剂,能够有效提高所合成材料的性能品质。本方法可以实现快速多次合成、提高产率、增强产品选择性的目的,是一种高效的MOFs材料合成方法。
在前期研究中发现常用的硝酸铜和硝酸铝等原料在反应过程中去质子化率低,影响了Cu-Al前驱体材料的合成速率,使得材料产率低,并且不利于Cu、 Al金属活性位点的分散,进而影响材料的催化效率。因此,经过大量实验探索,本发明筛选出了特定的长链金属Cu、Al盐,有效地提高了Cu-Al前驱体合成效率。实验结果表明该方法可以增强Cu、Al金属间的相互作用,并且提高了Cu、 Al金属离子在材料内的分散度,有利于提高材料的催化性能。
此外,本专利的研究人员进一步发现,在将MnO2引入Cu-Al前驱体的制备过程中,通过加入特定的表面活性剂作为分子诱导剂,能够有效促进Mn前驱体的溶解和分散,充分诱导Mn元素进入Cu-Al前驱体结构内,最终合成出新型的均匀、稳定、具有高催化性能的MnO2/Cu-Al-BTC三元金属有机骨架化合物。
本发明的技术方案:
一种MnO2/Cu-Al-BTC三元金属有机骨架材料的制备方法,步骤如下:
(1)Cu-Al前驱体的制备
将均苯三甲酸H3BTC溶于体积比为25:3:2-35:4:1的无水乙醇、苯甲酸、乙酸混合液中,配制成浓度为0.16-0.18mol/L的均苯三甲酸溶液,磁力搅拌器上混合搅拌至溶解;之后加入氯化二羟基-双四甲基亚乙基二胺铜(II)和(十八烷-9-烯基乙酰乙酸根合-O1’,O3)二丙烷-2-醇合铝以及超纯水,继续搅拌至完全溶解;其中铜盐、铝盐与均苯三甲酸的摩尔比为6.78:1.24:4.8-1.32:1.24:7.2,无水乙醇与超纯水的体积比为0.71:1-1.4:1;将上述混合体系置于微波反应器中,在 100℃-160℃下反应0.5-1.5h,得到蓝色液体;将反应物离心收集,并依次用无水乙醇和超纯水进行纯化;最后,将反应物进行真空干燥,得到蓝色粉末状固体;
(2)Mn前驱体溶液的制备
将四水合氯化锰(MnCl2·4H2O)固体放于无水乙醇中,搅拌至溶解,配置成Mn离子浓度为0.14-0.34mol/L的氯化锰溶液;向溶液中加入的硬脂酸甲酯聚氧乙烯醚磺酸盐(FMES)和辛基酚聚氧乙烯醚(OP-6)两种分子诱导剂的混合液,在室温下磁力搅拌0.5-1.5h;其中FMES与OP-6的摩尔比为1:0.83-1:3.32,氯化锰溶液与诱导剂混合液的体积比为3.33:1-6:1;
(3)MnO2/Cu-Al-BTC的制备
将Cu-Al前驱体材料加入至Mn前驱体溶液中,配制成浓度为 0.025-0.075g/mL的溶液,在室温下磁力搅拌3-5h;将混合液过滤,取过滤后的固体,将其置于烘箱中,设定加热温度100-120℃,加热时间8-12h;待固体样品冷却至室温后取出,在240-260℃、N2气氛下使用管式炉煅烧样品2-3h,制备出深蓝色MnO2/Cu-Al-BTC粉末状样品。
步骤(1)中,真空干燥的条件为90-110℃,10-12h。
一种MnO2/Cu-Al-BTC三元金属有机骨架材料在CO选择性催化还原反应脱硝(CO-SCR)方面的应用。
本发明的有益效果:本发明提出利用微波辅助加热-浸渍联合制备 MnO2/Cu-Al-BTC材料的方法,获得的样品样品颗粒均匀,粒径约为0.2-0.5μm,且形貌完整,比表面积为647m2g-1。CO-SCR测试结果显示,MnO2/Cu-Al-BTC 催化剂在260-375℃温度区间内取得了90-96%的脱硝效率,低温活性较好,且具有较高的热稳定性。该方法反应时间短、能耗低、催化效果好,是一种新型、高效、便捷的MOFs催化剂制备方法。
附图说明
图1是不同比例MnO2/Cu-Al-BTC材料的XRD图;
图2是不同比例MnO2/Cu-Al-BTC材料的SEM图;(a)MnO2/Cu-Al-BTC(A), (b)MnO2/Cu-Al-BTC(B);
图3是不同比例MnO2/Cu-Al-BTC材料的N2吸脱附图;
图4是不同比例MnO2/Cu-Al-BTC材料的TGA图;
图5是MnO2/Cu-Al-BTC催化剂的H2-TPR图;
图6是不同比例MnO2/Cu-Al-BTC催化剂的CO-SCR活性测试曲线。
具体实施方式
以下内容为本发明专利的具体实施过程。
实施例1:Cu-Al前驱体材料的制备方法
取4.8mmol,1.0293g均苯三甲酸(H3BTC)试剂与25mL无水乙醇、3mL 苯甲酸、2mL乙酸放入100mL烧杯,将烧杯放置在磁力搅拌器上混合搅拌至溶解;向烧杯中加入6.78mmol,3.1488g氯化二羟基-双四甲基亚乙基二胺铜(II)、 1.24mmol,0.6159g(十八烷-9-烯基乙酰乙酸根合-O1’,O3)二丙烷-2-醇合铝及 35mL超纯水,置于磁力搅拌器上混合搅拌0.5h至溶解;将盛有混合液的烧杯置于微波反应器中,在100℃下反应0.5h,待自然冷却至室温后,离心收集反应物,离心收集条件为转速:9000r/min,时间:5min。
将收集到的样品用30mL无水乙醇分别洗3次,每次都离心收集。再将样品用50mL超纯水分别洗3次,每次也都离心收集。将收集的样品放入真空干燥箱中,在90℃下干燥10个小时,得到蓝色粉末状固体。
实施例2:Mn前驱体溶液的制备方法
取4.2mmol,0.8312g四水合氯化锰(MnCl2·4H2O)固体放于30mL无水乙醇中,置于磁力搅拌器上混合搅拌0.5h至溶解,配置成Mn离子浓度为 0.14mol/L的溶液。向溶液中加入5mL摩尔比为1:0.83的FMES和OP-6的混合液,在室温下搅拌0.5h。
实施例3:MnO2/Cu-Al-BTC的合成方法
取0.3g Cu-Al前驱体材料与12ml Mn前驱体溶液在烧杯中混合,在室温下磁力搅拌3h。将混合液过滤,取过滤后的固体在100℃下加热8h。待固体样品冷却至室温后取出,在240℃、N2气氛下使用管式炉煅烧样品2h,得到深蓝色MnO2/Cu-Al-BTC粉末状样品。
实施例4:
在本发明实施例1中将无水乙醇、苯甲酸、乙酸的用量分别调整为30mL、 3.5mL、1.5mL,均苯三甲酸的用量增加到5.95mmol,其他原料用量以及实验步骤保持不变,制得深蓝色MnO2/Cu-Al-BTC材料。
实施例5:
在本发明实施例1中将无水乙醇、苯甲酸、乙酸的用量分别调整为35mL、 4mL、1mL,均苯三甲酸的用量增加到7.2mmol,其他原料用量以及实验步骤保持不变,制得深蓝色MnO2/Cu-Al-BTC材料。
实施例6:
在本发明实施例1中将氯化二羟基-双四甲基亚乙基二胺铜(II)与(十八烷-9- 烯基乙酰乙酸根合-O1’,O3)二丙烷-2-醇合铝的用量分别调整为3.88mmol、 1.24mmol,超纯水的用量改为30mL,微波反应温度增加到130℃,反应时间增加到1h,真空干燥温度增加到100℃,干燥时间增加到11h,其他原料用量以及实验步骤保持不变,制得深蓝色MnO2/Cu-Al-BTC材料。
实施例7:
在本发明实施例1中将氯化二羟基-双四甲基亚乙基二胺铜(II)与(十八烷-9- 烯基乙酰乙酸根合-O1’,O3)二丙烷-2-醇合铝的用量分别调整为1.32mmol、 1.24mmol,超纯水的用量改为25mL,微波反应温度增加到160℃,反应时间增加到1.5h,真空干燥温度增加到110℃,干燥时间增加到12h,其他原料用量以及实验步骤保持不变,制得深蓝色MnO2/Cu-Al-BTC材料。
实施例8:
在本发明实施例2中将四水合氯化锰用量增加到7.2mmol,FMES和OP-6 混合液的用量增加到7mL、摩尔比改为1:2.08,在室温下磁力搅拌1h,其他原料用量以及实验步骤保持不变,制得深蓝色MnO2/Cu-Al-BTC材料。
实施例9:
在本发明实施例2中将四水合氯化锰用量增加到10.2mmol,FMES和OP-6 混合液的用量增加到9mL、摩尔比改为1:3.32,在室温下磁力搅拌1.5h,其他原料用量以及实验步骤保持不变,制得深蓝色MnO2/Cu-Al-BTC材料。
实施例10:
在本发明实施例3中将Cu-Al前驱体用量增加到0.6g,在室温下磁力搅拌时间增加到4h,其他原料用量以及实验步骤保持不变,制得深蓝色 MnO2/Cu-Al-BTC材料。
实施例11:
在本发明实施例3中将Cu-Al前驱体用量增加到0.9g,在室温下磁力搅拌时间增加到5h,其他原料用量以及实验步骤保持不变,制得深蓝色 MnO2/Cu-Al-BTC材料。
实施例12:
在本发明实施例3中将加热温度增加到110℃,加热时间10h。使用管式炉煅烧时将煅烧温度增加到250℃、煅烧时间增加到2.5h,其他原料用量以及实验步骤保持不变,制得深蓝色MnO2/Cu-Al-BTC材料。
实施例13:
在本发明实施例3中将加热温度增加到120℃,加热时间12h。使用管式炉煅烧时将煅烧温度增加到260℃、煅烧时间增加到3h,其他原料用量以及实验步骤保持不变,制得深蓝色MnO2/Cu-Al-BTC材料。
Claims (3)
1.一种MnO2/Cu-Al-BTC三元金属有机骨架材料的制备方法,其特征在于,步骤如下:
(1)Cu-Al前驱体的制备
将均苯三甲酸H3BTC溶于体积比为25:3:2-35:4:1的无水乙醇、苯甲酸、乙酸混合液中,配制成浓度为0.16-0.18mol/L的均苯三甲酸溶液,磁力搅拌器上混合搅拌至溶解;之后加入氯化二羟基-双四甲基亚乙基二胺铜(II)和(十八烷-9-烯基乙酰乙酸根合-O1’,O3)二丙烷-2-醇合铝以及超纯水,继续搅拌至完全溶解;其中铜盐、铝盐与均苯三甲酸的摩尔比为6.78:1.24:4.8-1.32:1.24:7.2,无水乙醇与超纯水的体积比为0.71:1-1.4:1;将上述混合体系置于微波反应器中,在100℃-160℃下反应0.5-1.5h,得到蓝色液体;将生成物离心收集,并依次用无水乙醇和超纯水进行纯化;最后,进行真空干燥,得到蓝色粉末状固体;
(2)Mn前驱体溶液的制备
将四水合氯化锰固体放于无水乙醇中,搅拌至溶解,配置成Mn离子浓度为0.14-0.34mol/L的氯化锰溶液;向溶液中加入硬脂酸甲酯聚氧乙烯醚磺酸盐FMES和辛基酚聚氧乙烯醚OP-6两种分子诱导剂的混合液,在室温下磁力搅拌0.5-1.5h;其中FMES与OP-6的摩尔比为1:0.83-1:3.32,氯化锰溶液与诱导剂混合液的体积比为3.33:1-6:1;
(3)MnO2/Cu-Al-BTC的制备
将Cu-Al前驱体材料加入至Mn前驱体溶液中,配制成浓度为0.025-0.075g/mL的溶液,在室温下磁力搅拌3-5h;将混合液过滤,取过滤后的固体,将其置于烘箱中,设定加热温度100-120℃,加热时间8-12h;待固体样品冷却至室温后取出,在240-260℃、N2气氛下使用管式炉煅烧样品2-3h,制备出深蓝色MnO2/Cu-Al-BTC粉末状样品。
2.根据权利要求1所述的制备方法,其特征在于,步骤(1)中,真空干燥的条件为90-110℃,10-12h。
3.一种采用如权利要求1或2所述的制备方法得到的MnO2/Cu-Al-BTC三元金属有机骨架材料在CO选择性催化还原反应脱硝方面的应用。
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