CN108298499B - 一种水溶性金属配合物催化甲酸分解放氢的方法 - Google Patents
一种水溶性金属配合物催化甲酸分解放氢的方法 Download PDFInfo
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- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 title claims abstract description 100
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 title claims abstract description 50
- 235000019253 formic acid Nutrition 0.000 title claims abstract description 50
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title claims abstract description 37
- 239000001257 hydrogen Substances 0.000 title claims abstract description 33
- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 33
- 150000004696 coordination complex Chemical class 0.000 title claims abstract description 22
- 238000000034 method Methods 0.000 title claims abstract description 21
- 239000003054 catalyst Substances 0.000 claims abstract description 41
- 239000007789 gas Substances 0.000 claims abstract description 18
- 239000007864 aqueous solution Substances 0.000 claims abstract description 12
- 229910052751 metal Inorganic materials 0.000 claims abstract description 12
- 239000002184 metal Substances 0.000 claims abstract description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 33
- 239000000243 solution Substances 0.000 claims description 30
- 238000006243 chemical reaction Methods 0.000 claims description 20
- 239000004280 Sodium formate Substances 0.000 claims description 17
- 239000003446 ligand Substances 0.000 claims description 17
- HLBBKKJFGFRGMU-UHFFFAOYSA-M sodium formate Chemical compound [Na+].[O-]C=O HLBBKKJFGFRGMU-UHFFFAOYSA-M 0.000 claims description 17
- 235000019254 sodium formate Nutrition 0.000 claims description 17
- 239000011261 inert gas Substances 0.000 claims description 12
- 150000001408 amides Chemical class 0.000 claims description 8
- 230000003197 catalytic effect Effects 0.000 claims description 8
- 229910052741 iridium Inorganic materials 0.000 claims description 8
- 229910052707 ruthenium Inorganic materials 0.000 claims description 8
- 239000012018 catalyst precursor Substances 0.000 claims description 6
- 238000001914 filtration Methods 0.000 claims description 6
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- HFPZCAJZSCWRBC-UHFFFAOYSA-N p-cymene Chemical compound CC(C)C1=CC=C(C)C=C1 HFPZCAJZSCWRBC-UHFFFAOYSA-N 0.000 claims description 4
- 238000005349 anion exchange Methods 0.000 claims description 3
- 150000001450 anions Chemical class 0.000 claims description 3
- 150000002504 iridium compounds Chemical class 0.000 claims description 3
- 150000003304 ruthenium compounds Chemical class 0.000 claims description 3
- 238000003756 stirring Methods 0.000 claims description 3
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical group [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical group [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 2
- 229910052796 boron Chemical group 0.000 claims description 2
- 150000001805 chlorine compounds Chemical group 0.000 claims description 2
- 125000000058 cyclopentadienyl group Chemical group C1(=CC=CC1)* 0.000 claims description 2
- ZSWFCLXCOIISFI-UHFFFAOYSA-N endo-cyclopentadiene Natural products C1C=CC=C1 ZSWFCLXCOIISFI-UHFFFAOYSA-N 0.000 claims description 2
- HQVFCQRVQFYGRJ-UHFFFAOYSA-N formic acid;hydrate Chemical compound O.OC=O HQVFCQRVQFYGRJ-UHFFFAOYSA-N 0.000 claims description 2
- YUWFEBAXEOLKSG-UHFFFAOYSA-N hexamethylbenzene Chemical compound CC1=C(C)C(C)=C(C)C(C)=C1C YUWFEBAXEOLKSG-UHFFFAOYSA-N 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 125000002097 pentamethylcyclopentadienyl group Chemical group 0.000 claims description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 2
- 238000007599 discharging Methods 0.000 claims 1
- 238000006555 catalytic reaction Methods 0.000 abstract description 10
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- 238000000354 decomposition reaction Methods 0.000 abstract description 8
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- 229910052757 nitrogen Inorganic materials 0.000 description 5
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- 238000002390 rotary evaporation Methods 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 239000011232 storage material Substances 0.000 description 3
- 229910021640 Iridium dichloride Inorganic materials 0.000 description 2
- 239000001569 carbon dioxide Substances 0.000 description 2
- 229910002092 carbon dioxide Inorganic materials 0.000 description 2
- 238000002485 combustion reaction Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 238000005374 membrane filtration Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- -1 silver tetrafluoroborate Chemical compound 0.000 description 2
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000006392 deoxygenation reaction Methods 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
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- 239000002803 fossil fuel Substances 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
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- 239000011541 reaction mixture Substances 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 239000010948 rhodium Substances 0.000 description 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
- 229910001494 silver tetrafluoroborate Inorganic materials 0.000 description 1
- 239000011949 solid catalyst Substances 0.000 description 1
- 230000009967 tasteless effect Effects 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
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Abstract
本发明提供了一种水溶性金属配合物催化甲酸分解放氢的方法,属于能源与均相催化技术领域。本发明合成了一系列水溶性较好的金属配合物作为催化甲酸分解的催化剂,并将其应用于甲酸分解放氢。本发明的优点是:该系列金属配合物催化剂的制备方法简单,成本较低,能在较为适宜的pH条件下快速催化甲酸完全分解直至无气体放出,且无毒副产物生成。该催化反应完全在水溶液中进行,避免了使用有机溶剂带来的污染。
Description
技术领域
本发明属于能源与均相催化技术领域,涉及到均相催化甲酸分解放氢,特别涉及到采用该类金属配合物催化甲酸分解放氢的方法。
背景技术
随着化石燃料的大量消耗,不仅对环境造成了较为严重的污染,同时能源问题也日益严重,为了实现经济的可持续性发展,开发出一种绿色、环保、高效、可再生的新型能源受到了广泛关注。氢气作为一种清洁高效的绿色能源,它具有以下优点:氢元素来源比较广泛、燃烧放出热量高、燃烧产物仅为水对环境无污染。虽然氢气具有许多的优点,但目前仍未能广泛应用,面临的一个主要问题就是氢气的运输问题。因为在常温常压下,氢气是一种易燃、易爆、易扩散,且无色无味的气体。通常需要通过高压进行存储,存储效率低,能量消耗大,且氢气易与金属产生氢脆现象,这些问题很大程度上制约了氢气的应用。因此,解决氢气的储存于运输问题成为氢气广泛应用的关键问题。
在目前众多储氢材料中,甲酸是一种理想的储氢材料。甲酸具有较高含氢密度(4.4wt%),而且它在室温下呈液态,便于进行储存和运输。而且,甲酸可以通过二氧化碳加氢方法制得,从而具有良好的可再生性,是一种非常理想的储氢材料(Grasemann,M.;Laurenczy,G.Energy Environ.Sci.2012,5,8171-8181)。近几年来,运用过渡金属催化甲酸分解放氢备受关注,特别是对铱、铑、钌等金属配合物的研究屡见报道。其中Pidko,Xiao和Himeda等人开发的催化剂展示出优异的催化活性(Wang,W.-H.;Himeda,Y.;Muckerman,J.T.;Manbeck,G.F.;Fujita,E.;Chem.Rev.2015,115,12936-12973)。2017年,Himeda组提出一种新型的催化剂体系,即利用酰胺作为配体合成催化剂,具有较好的催化活性(Ryoichi Kanega,Naoya Onishi,David J.Szalda,Yuichiro Himeda;ACS Catal.2017,7,6426-6429)。本专利在该文献的基础上研究了一类新型的酰胺作为配体的催化剂,通过实验探究发现该类催化剂具有非常好的催化活性。
发明内容
本发明所要解决的技术问题在于针对甲酸分解放出氢气,提供了一类新型水溶性金属(包括Ir,Ru)配合物催化剂来催化甲酸放氢。该种水溶性金属配合物催化剂的制备方法简单,成本较低,能在较低温度下催化甲酸完全分解放出氢气,在催化甲酸分解的过程中具有良好的催化效率,转化频率TOF值最高达到49270h-1。该催化反应完全在水溶液中进行,避免了使用有机溶剂带来的污染。
本发明的技术方案:
一种水溶性金属配合物催化甲酸分解放氢的方法,所述的水溶性金属配合物的结构式如下式(I)和式(II):
式中:L=H2O或Cl;
M=Ir或Ru;
Ar=苯、六甲基苯、对甲基异丙基苯、五甲基环戊二烯基(Cp*)或环戊二烯基(Cp);
W为氯负离子、硫酸根或四氟化硼阴离子;
n=负整数、0或正整数;
在惰性气体的保护下,60℃温度条件下,向甲酸/甲酸钠溶液中加入水溶性金属配合物催化剂,催化体系立即放出气体,且在40~120min内甲酸完全分解放出氢气。
其中,甲酸/甲酸钠溶液为浓度范围在1~12mol/L之间的甲酸水溶液或甲酸与甲酸钠的混合水溶液,体积混合比例为10:0.1~4:6,不同的甲酸/甲酸钠溶液对应不同的pH。
所述的水溶性金属配合物的制备方法,步骤如下:
按照摩尔比为按照摩尔比为1~2:1将酰胺配体和催化剂前体金属铱化合物或催化剂前体金属钌化合物加入到无水甲醇中,在惰性气体保护下,65~80℃温度条件下搅拌反应9~12h,反应结束后,冷却至室温,对反应液进行过滤,并收集滤渣,真空干燥除去甲醇,得到水溶性金属配合物催化剂I。再根据水溶性Ir、Ru金属配合物催化剂的具体形式,进一步进行阴离子交换。
本发明的有益效果:
1、本发明制得的金属配合物催化剂制备方法比较简单,能在较低温度下快速催化甲酸完全分解放出氢气和二氧化碳;催化剂在催化甲酸分解放氢过程中取得了良好的催化效率,60℃时,转化频率TOF值高达49270h-1,且无CO毒副产物生成。
2、该催化反应完全在水溶液中进行。解决了目前大多数用于甲酸分解放氢的催化剂水溶性差及放氢不完全的难题,为氢能的大规模利用提供了一种新的思路。
附图说明
图1是式(I)中R1=OH,其中R3=H,R4=OH作为配体,M=Ir的催化剂[Cp*Ir(C11N2H10O2)Cl]Cl的1H NMR谱图。
图2是式(I)中R1=H,其中R3=H,R4=OH作为配体,M=Ir的催化剂Cp*Ir(C11N2H9O)Cl的1H NMR谱图。
图3是式(I)中R1=OH,其中R3=H,R4=H作为配体,M=Ir的催化剂[Cp*Ir(C11N2H10O)Cl]Cl的1H NMR谱图。
图4是式(II)中R1=H,其中R6=H,R7=OH,作为配体,M=Ir的催化剂[Cp*Ir(C12N2H12O)Cl]Cl的1H NMR谱图。
图5是催化剂[Cp*Ir(C11N2H9O)OH2]BF4催化甲酸分解在不同pH下放出气体体积随时间的变化曲线。
图6是催化剂[Cp*Ir(C11N2H9O)OH2]BF4催化甲酸分解放氢的TOF随pH的变化曲线。
具体实施方式
以下结合附图和技术方案,进一步说明本发明的具体实施方式。
实施例1
式(I)中R1=OH,其中R3=H,R4=OH作为配体,M=Ir的催化剂[Cp*Ir(C11N2H10O2)Cl]Cl的制备及其催化甲酸分解放氢的方法:
(1)将酰胺配体(28.95mg,0.1250mmol)和[Cp*IrCl2]2(50.00mg,0.0625mmol)加入到无水甲醇(10mL)中,惰性气体保护下,升温至65℃反应液中出现大量沉淀,搅拌反应12h。反应结束后,冷却至室温,用膜过滤装置过滤反应液,收集滤渣,得黄色固体催化剂产品,真空干燥除去甲醇。通过核磁谱图(图1)对结构进行表征。
(2)配制1mol/L的甲酸和甲酸钠溶液,惰性气体保护下,对水溶液进行脱气处理,步骤如下:按1:1的体积比配制甲酸/甲酸钠的水溶液,抽真空充惰性气体操作连续3次;在惰性气体保护下,在液氮中冷冻至固体,抽真空条件下,缓慢升温脱除水溶液中溶解的氧气,重复该步骤3次;然后将冷冻脱氧后的水溶液置于惰性气体保护下存储备用;
(3)氮气保护下,将冷冻脱氧后的10mL水溶液升温至60℃,然后称量1μmol(约0.64mg)的催化剂[Cp*Ir(C11N2H10O2)Cl]Cl,加入到反应溶液中,同时记录放出气体的体积和时间,直至无气体放出;根据放出气体的体积计算前10min的TOF;利用利用液相色谱检测反应溶液中剩余的甲酸浓度,计算催化反应的TON。
实施例2
式(I)中R1=H,其中R3=H,R4=OH作为配体,M=Ir的催化剂Cp*Ir(C11N2H9O)Cl的制备及其进行阴离子后催化甲酸分解放氢的方法:
(1)Cp*Ir(C11N2H9O)Cl催化剂的制备同实施例1中步骤(1)。将酰胺配体(26.99mg,0.1250mmol)和[Cp*IrCl2]2(50.00mg,0.0625mmol)加入到无水甲醇(10mL)中,惰性气体保护下,65℃搅拌反应9h。反应结束后,冷却至室温,用膜过滤装置过滤反应液,收集滤渣,真空干燥除去溶剂,得亮黄色固体Cp*Ir(C11N2H9O)Cl。通过核磁谱图(图2)对结构进行表征。
(2)催化剂与四氟硼酸银进行离子交换制备[Cp*Ir(C11N2H9O)OH2]BF4,取10mg催化剂Cp*Ir(C11N2H9O)Cl与四氟硼酸银按1:2的摩尔比避光搅拌2h,溶液中出现白色沉淀,膜过滤除去沉淀,将滤液旋蒸干燥,计算得到固体质量,用水溶解,得到催化剂的水溶液,对催化剂的水溶液进行冷冻脱氧,储存备用。
(3)对体积比为1:1的10mL的甲酸/甲酸钠溶液进行脱氧处理,同实施例1步骤(2)。
(4)氮气保护下,将冷冻脱氧后的10mL体积比为甲酸/甲酸钠溶液升温至60℃后,使用微型移液器将150μL催化剂溶液(0.5μmol)加入到反应液中,,同时记录放出气体的体积和时间,直至无气体放出,气体放出量与时间的关系如图5中pH=3.53的曲线所示;根据气体放出量计算催化反应初始10min的TOF;利用液相色谱检测反应溶液中剩余的甲酸浓度,计算催化反应的TON。
实施例3
式(I)中R1=OH,其中R3=H,R4=H作为配体,M=Ir的催化剂[Cp*Ir(C11N2H10O)Cl]Cl的制备及其催化甲酸分解放氢的方法:
(1)将酰胺配体(17.57mg,0.082mmol)和[Cp*IrCl2]2(32.64mg,0.041mmol)加入到无水甲醇(10mL)中,惰性气体保护下,升温至65℃,升温过程中固体逐渐溶解,搅拌反应12h。最终得到明黄色的反应液,最终旋蒸除去溶剂得到催化剂产品。通过核磁谱图(图3)对结构进行表征。
(2)对体积比为1:1的10mL的甲酸/甲酸钠溶液进行脱氧处理,同实施例1步骤(2)。
(3)氮气保护下,将冷冻脱氧后的甲酸/甲酸钠溶液升温至60℃后,向反应瓶中加入1μmol(约0.61mg)的催化剂[Cp*Ir(C11N2H10O)Cl]Cl,同时记录放出气体体积和时间,直至无气体放出;根据放出气体量计算催化反应的初始10min的TOF,利用液相色谱检测反应溶液中剩余的甲酸浓度,计算催化反应的TON。
实施例4
式(II)中R1=H,其中R6=H,R7=OH,作为配体,M=Ir的催化剂[Cp*Ir(C12N2H12O)Cl]Cl的制备及其催化甲酸分解放氢的方法:
(1)将配体3a(28.63mg,0.0125mmol)和[Cp*IrCl2]2(50mg,0.0625mmol)加入到无水甲醇(10mL)中,惰性气体保护下,升温至65℃,升温过程中固体逐渐溶解,搅拌反应12h。最终得到明黄色的反应液,最终旋蒸除去溶剂得到催化剂产品。通过核磁谱图(图4)对结构进行表征。
(2)对体积比为1:1的10mL的甲酸/甲酸钠溶液进行脱氧处理,同实施例1步骤(2)。
(3)氮气保护下,将冷冻脱氧后的甲酸/甲酸钠溶液升温至60℃后,向反应液中加入1μmol(约0.63mg)的催化剂[Cp*Ir(C12N2H12O)Cl]Cl,同时记录放出气体体积和时间,直至无气体放出;根据放出气体量计算催化反应的初始10min的TOF,利用液相色谱检测反应溶液中剩余的甲酸浓度,计算催化反应的TON。
Claims (7)
2.根据权利要求1所述的方法,其特征在于,甲酸/甲酸钠溶液为浓度范围在1~12mol/L之间的甲酸水溶液或甲酸与甲酸钠的混合水溶液,二者的体积混合比为10:0.1~4:6。
3.根据权利要求1或2所述的方法,其特征在于,所述的甲酸与水溶性Ir或Ru金属配合物的摩尔比为10000~20000。
4.根据权利要求1或2所述的方法,其特征在于,所述的水溶性金属配合物的制备方法,步骤如下:
按照摩尔比为1~2:1将酰胺配体和催化剂前体金属铱化合物或催化剂前体金属钌化合物加入到无水甲醇中,在惰性气体保护下,65~80℃温度条件下搅拌反应9~12h,反应结束后,冷却至室温,对反应液进行过滤,并收集滤渣,真空干燥除去甲醇,得到水溶性金属配合物催化剂I。
5.根据权利要求3所述的方法,其特征在于,所述的水溶性金属配合物的制备方法,步骤如下:
按照摩尔比为1~2:1将酰胺配体和催化剂前体金属铱化合物或催化剂前体金属钌化合物加入到无水甲醇中,在惰性气体保护下,65~80℃温度条件下搅拌反应9~12h,反应结束后,冷却至室温,对反应液进行过滤,并收集滤渣,真空干燥除去甲醇,得到水溶性金属配合物催化剂I。
6.根据权利要求4所述的方法,其特征在于,再根据水溶性Ir或Ru金属配合物催化剂的具体形式,进一步进行阴离子交换。
7.根据权利要求5所述的方法,其特征在于,再根据水溶性Ir或Ru金属配合物催化剂的具体形式,进一步进行阴离子交换。
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