CN108440604B - 一种双核铱-铂配合物、其制备方法及其应用 - Google Patents
一种双核铱-铂配合物、其制备方法及其应用 Download PDFInfo
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- HWLDNSXPUQTBOD-UHFFFAOYSA-N platinum-iridium alloy Chemical compound [Ir].[Pt] HWLDNSXPUQTBOD-UHFFFAOYSA-N 0.000 title claims abstract description 36
- 238000002360 preparation method Methods 0.000 title abstract description 5
- 238000010668 complexation reaction Methods 0.000 title description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 23
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 21
- 239000001257 hydrogen Substances 0.000 claims abstract description 21
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 20
- 239000011259 mixed solution Substances 0.000 claims abstract description 12
- KGZSSIFFYUBVOX-UHFFFAOYSA-N 2-[4-(trifluoromethyl)phenyl]pyridine Chemical group C1=CC(C(F)(F)F)=CC=C1C1=CC=CC=N1 KGZSSIFFYUBVOX-UHFFFAOYSA-N 0.000 claims abstract description 6
- 108010088694 phosphoserine aminotransferase Proteins 0.000 claims abstract description 6
- YSHMQTRICHYLGF-UHFFFAOYSA-N 4-tert-butylpyridine Chemical compound CC(C)(C)C1=CC=NC=C1 YSHMQTRICHYLGF-UHFFFAOYSA-N 0.000 claims abstract description 4
- 239000007983 Tris buffer Substances 0.000 claims abstract description 4
- 239000000126 substance Substances 0.000 claims abstract description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 45
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 36
- 239000000203 mixture Substances 0.000 claims description 19
- 230000001699 photocatalysis Effects 0.000 claims description 18
- 239000002243 precursor Substances 0.000 claims description 16
- 238000006243 chemical reaction Methods 0.000 claims description 15
- -1 platinum (II) hexafluorophosphate Chemical compound 0.000 claims description 14
- 229910021595 Copper(I) iodide Inorganic materials 0.000 claims description 12
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 12
- LSXDOTMGLUJQCM-UHFFFAOYSA-M copper(i) iodide Chemical compound I[Cu] LSXDOTMGLUJQCM-UHFFFAOYSA-M 0.000 claims description 12
- MILUBEOXRNEUHS-UHFFFAOYSA-N iridium(3+) Chemical compound [Ir+3] MILUBEOXRNEUHS-UHFFFAOYSA-N 0.000 claims description 11
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 9
- 230000009467 reduction Effects 0.000 claims description 9
- 239000007864 aqueous solution Substances 0.000 claims description 8
- 238000004519 manufacturing process Methods 0.000 claims description 8
- 238000000034 method Methods 0.000 claims description 7
- FYEQEHADNCBYTO-UHFFFAOYSA-N 2-(4-ethynylphenyl)-1H-imidazo[4,5-f][1,10]phenanthroline Chemical compound C(#C)C1=CC=C(C=C1)C=1NC=2C(=C3C=CC=NC3=C3N=CC=CC=23)N=1 FYEQEHADNCBYTO-UHFFFAOYSA-N 0.000 claims description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 4
- 239000007795 chemical reaction product Substances 0.000 claims description 4
- 239000003480 eluent Substances 0.000 claims description 4
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- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 abstract description 18
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 9
- 239000000047 product Substances 0.000 description 6
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- 239000003504 photosensitizing agent Substances 0.000 description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- 239000003054 catalyst Substances 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000011941 photocatalyst Substances 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 3
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- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical group [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 229910052697 platinum Inorganic materials 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
- 229910052724 xenon Inorganic materials 0.000 description 2
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 2
- 238000005160 1H NMR spectroscopy Methods 0.000 description 1
- DRGAZIDRYFYHIJ-UHFFFAOYSA-N 2,2':6',2''-terpyridine Chemical compound N1=CC=CC=C1C1=CC=CC(C=2N=CC=CC=2)=N1 DRGAZIDRYFYHIJ-UHFFFAOYSA-N 0.000 description 1
- JFJNVIPVOCESGZ-UHFFFAOYSA-N 2,3-dipyridin-2-ylpyridine Chemical compound N1=CC=CC=C1C1=CC=CN=C1C1=CC=CC=N1 JFJNVIPVOCESGZ-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 241000282414 Homo sapiens Species 0.000 description 1
- 238000005481 NMR spectroscopy Methods 0.000 description 1
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- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000003034 coal gas Substances 0.000 description 1
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- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
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- C07F15/00—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table
- C07F15/0006—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table compounds of the platinum group
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- B01J31/181—Cyclic ligands, including e.g. non-condensed polycyclic ligands, comprising at least one complexing nitrogen atom as ring member, e.g. pyridine
- B01J31/184—Cyclic ligands, including e.g. non-condensed polycyclic ligands, comprising at least one complexing nitrogen atom as ring member, e.g. pyridine mixed aromatic/aliphatic ring systems, e.g. indoline
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Abstract
本发明公开了一种双核铱‑铂配合物、其制备方法及其应用,一种双核铱‑铂配合物,其化学通式为(tmfppy)2Ir‑EPIP‑PtL,其中,tmfppy为2‑(4‑(三氟甲基)苯基)吡啶,EPIP为2[4‑乙炔基苯基]‑1H‑咪唑并[4,5‑f][1,10]邻菲罗啉,L为2,2’:6’,2”‑三(4‑叔丁基)吡啶。本发明铱‑铂双核配合物,可以在丙酮和水的混合溶液中,可见光照射下,催化还原水制备氢气。
Description
技术领域
本发明涉及一种双核铱-铂配合物、其制备方法及其应用,属于光催化剂领域。
背景技术
为了应对由于大量消耗化石能源导致的能源危机和环境污染问题,人类将目光转向清洁、低碳能源,大力开发太阳能、风能、地热等绿色可再生能源,改善原本以煤炭、石油、天然气为主的能源消费结构,为世界快速发展和加速繁荣的能源需求提供保障,同时降低排放,实现现代化社会的绿色可持续发展。
在各种可再生能源中,太阳能作为水能、风能等多数可再生能源的来源,总量丰富,能量提供持续时间长久,辐照分布地域广,是未来满足社会发展的理想能源来源。但是太阳能供能受限于其不连续性,需要将太阳能转化为其他诸如热能、电能、氢能等连续稳定的能源进行利用。无碳氢作为环境友好的可再生能源,燃烧效率高、产物只有水,是理想的备选能源。传统的制氢工艺主要从化石能源中提取或者电解获得氢气,污染较大或者电耗较高。人工光合成技术模仿自然界光合作用,利用光能催化地球储量丰富的水还原,水分解产生氢能。
传统的均相光催化分解水需要使用光敏剂、光催化剂、牺牲剂,且存在可见光吸收能力差、催化速率缓慢、主要组分易降解、组分过多等问题。因此急需开发新型光敏剂和光催化剂等。
发明内容
为了解决现有技术中的不足,本发明提供一种双核铱-铂配合物、其制备方法及其应用,本申请双核铱-铂配合物具有可见光响应,可作为光催化水还原的光敏剂和催化剂运用到光分解水制氢中。
为解决上述技术问题,本发明所采用的技术方案如下:
一种双核铱-铂配合物,其化学通式为(tmfppy)2Ir-EPIP-PtL,其中,tmfppy为2-(4-(三氟甲基)苯基)吡啶,EPIP为2[4-乙炔基苯基]-1H-咪唑并[4,5-f][1,10]邻菲罗啉,L为2,2’:6’,2”-三(4-叔丁基)吡啶。
上述三价铱部分的通式中,tmfppy为2-(4-(三氟甲基)苯基)吡啶;铱-铂连接部分的通式中,EPIP为2[4-乙炔基苯基]-1H-咪唑并[4,5-f][1,10]邻菲罗啉;二价铂部分的通式中,L为2,2’:6’,2”-三(4-叔丁基)吡啶。
本申请利用桥联配体将多元均相光催化产氢***中的光吸收组分和光催化位点连接起来,使得光催化产氢***简化为由单个分子组成的超分子光催化产氢***,不仅避免了扩散过程,使得光催化反应摆脱对碰撞概率的依赖性,降低在电子迁移方面受到的限制,还为新型多核光催化剂的开发和均相光催化***未来的研究提供新思路。
本申请铱-铂双核配合物的结构式如下:
上述双核铱-铂配合物的制备方法,将铱(III)前驱体和六氟磷酸铂(Ⅱ)前驱体溶解于由二氯甲烷和三乙胺组成的混合溶液中,在避光环境下搅拌反应30±5分钟,随后加入碘化亚铜,于避光处加热回流搅拌反应100-140小时,反应结束后,冷却至室温再加入六氟磷酸铵水溶液继续搅拌反应30±5分钟,将反应产物萃取提纯,获得铱-铂双核配合物。
本申请铱(III)指铱为三价铱;铂(Ⅱ)指铂为二价铂。
为了提高产品的催化效果,铱(Ⅲ)前驱体为Ir(tmfppy)2EPIP,其中,tmfppy为2-(4-(三氟甲基)苯基)吡啶,EPIP为2[4-乙炔基苯基]-1H-咪唑并[4,5-f][1,10]邻菲罗啉。
优选,六氟磷酸铂(Ⅱ)前驱体为[Pt(tBu3terpy)Cl]PF6。
上述tBu指叔丁基,terpy指三联吡啶。
为了提高反应效率,同时保证所得产品的质量,铱(Ⅲ)前驱体和六氟磷酸铂(Ⅱ)前驱体的摩尔比为2:(3±0.5)。
为了进一步提高反应效率,二氯甲烷和三乙胺的摩尔比为:674:(113±10),三乙胺与铱(Ⅲ)前驱体的摩尔比为:105:(337±10)。
为了保证所得产品的催化效率,碘化亚铜在有机混合溶液中的浓度为(0.625±0.1)mg/mL,碘化亚铜和铱(Ⅲ)前驱体的相对用量为(100±10)g碘化亚铜/1molIr(tmfppy)2EPIP,六氟磷酸铵水溶液和碘化亚铜的相对用量为(1.5±0.5)mL/mg,六氟磷酸铵水溶液的浓度为(0.5±0.1)mol/L。
为了提高所得产品的纯度,萃取提纯方法为:将反应产物用二氯甲烷萃取、溶剂旋转蒸发干燥后,在硅胶柱中以体积比为(20±5):1的二氯甲烷和甲醇的混合液为洗脱剂进行色谱分离。
本申请双核铱-铂配合物可用于光催化还原水制氢中。
本发明的双核铱-铂配合物具有双功能,可以同时作为光敏剂和催化剂应用到光催化水还原制备氢气中,例如,将铱-铂配合物、三乙胺(TEA)或者三乙醇胺(TEOA)溶解在丙酮与水的混合溶液中,用盐酸调节溶液pH,在可见光照射下实现光催化还原水制备氢气,所述铱-铂双核配合物作为光敏剂和催化剂,三乙胺或者三乙醇胺作为牺牲剂。
本发明未提及的技术均参照现有技术。
有益效果:本发明提供了一种铱-铂双核配合物,可以在丙酮和水的混合溶液中,可见光照射下,催化还原水制备氢气,可同时作为光敏剂和催化剂,可见光吸收能力强,光催化25h后无任何降解现象,催化效率得到显著的提升。
附图说明
图1为实施例1的铱-铂双核配合物的H谱图;
图2为实施例1的铱-铂双核配合物的高分辨质谱图;
图3-4为实施例1的铱-铂双核配合物用于光催化还原水制备氢气的氢气产出图,图中acetone为丙酮。
具体实施方式
为了更好地理解本发明,下面结合实施例进一步阐明本发明的内容,但本发明的内容不仅仅局限于下面的实施例。
实施例1
将0.20mmol的Ir(tmfppy)2EPIP(200mg)和0.26mmol的[Pt(tBu3terpy)Cl]PF6(198.8mg)(摩尔比为2:2.6)溶解于由24mL二氯甲烷和8mL三乙胺(摩尔比为:674:113)组成的混合溶液中,在避光环境中加热回流搅拌反应30分钟,随后加入20mg碘化亚铜,继续在避光环境下加热回流搅拌反应5天,反应结束后,冷却至室温,加入20mL0.5M(mol/L)六氟磷酸铵水溶液,搅拌反应30分钟,用二氯甲烷萃取三次,每次100mL,在旋转蒸发仪中移除溶剂,然后在硅胶柱中以体积比为20:1的二氯甲烷和甲醇为洗脱剂进行色谱分离,得到铱-铂双核配合物。
将铱-铂双核配合物进行核磁共振(H谱图见图1),测得:1HNMR(DMSO,500MHz):δ14.40(1H,s),δ9.24(2H,d,J=7.4),δ9.06(2H,d,J=5.9),δ8.76(4H,d,J=6.5),δ8.50(2H,d,J=8.1),δ8.34(2H,d,J=8.2),δ8.24(2H,d,J=8.2),δ8.16(4H,s),δ8.05(2H,t,J=7.7),δ7.93(2H,d,J=2.9),δ7.76(2H,d,J=8.2),δ7.67(2H,s),δ7.45(2H,d,J=8.0),δ7.17(2H,t,J=6.6),δ6.44(2H,s),δ1.56(9H,s),δ1.47(18H,s).
将铱-铂双核配合物进行高分辨质谱检测(ESI-MS(CH3OH)见图2):m/z1551.58[M+H]+。
实施例2
将0.20mmol的Ir(tmfppy)2EPIP(200mg)和0.32mmol的[Pt(tBu3terpy)Cl]PF6(248.5mg)(摩尔比为2:3.2)溶解于由24mL二氯甲烷和8mL三乙胺(摩尔比为:674:113)组成的混合溶液中,在避光环境中加热回流搅拌反应28分钟,随后加入18mg碘化亚铜,继续在避光环境下加热回流搅拌反应100小时,反应结束后,冷却至室温,加入10mL0.5M六氟磷酸铵水溶液,搅拌反应32分钟,用二氯甲烷萃取三次,每次100mL,在旋转蒸发仪中移除溶剂,然后在硅胶柱中以体积比为20:1的二氯甲烷和甲醇为洗脱剂进行色谱分离,得到铱-铂双核配合物,所得产物的H谱图和质谱图与实施例1完全一致,因此不重复提供。
应用测试
将上述实施例1制得的铱-铂双核配合物用于光催化还原水制备氢气,测试方法为:将1μmol铱-铂双核配合物加入到含有0.18MTEOA(三乙醇胺)的丙酮/水(pH=9)的混合溶液中(100mL),改变丙酮/水的比例(v/v=5/5,8/2,9/1,95/5),将反应器中的空气抽空后,在300W的氙灯下照射(λ>420nm),反应生成的氢气经气相色谱定量分析,测试结果见图3。
由图3可以看出,含有1μmol铱-铂双核配合物不同溶液环境体系在光照24小时后生成氢气的量分别为1.27μmol、108.19μmol、236.93μmol、69.03μmol,可以看出铱-铂双核配合物具有光催化水还原产氢活性,并且在丙酮/水(v/v=9:1)的溶液环境中该***光催化水还原产氢活性更高,TON(转化数:反应物转化的摩尔数/催化剂的摩尔数)达到474(24小时测试)。
将上述实施例1制得的铱-铂双核配合物用于光催化还原水制备氢气,测试方法为:将1μmol铱-铂双核配合物加入到含有0.18M三乙醇胺(TEOA)的丙酮/水(v/v=9:1)的混合溶液中(100mL),用盐酸调整混合溶液的pH值,使得溶液pH值分别为5、6、7、8、9,将反应器中的空气抽空后,在300W的氙灯下照射(λ>420nm),反应生成的氢气经气相色谱定量分析,测试结果见图4。
由图4可以看出,1μmol铱-铂双核配合物所在的含有0.18M三乙醇胺(TEOA)作为牺牲剂,溶液pH值不同的体系在光照8小时后生成氢气的量分别为2.59μmol(pH=5)、24.39μmol(pH=6)、29.09μmol(pH=7)、70.47μmol(pH=8)、167.19μmol(pH=9),可以看出铱-铂双核配合物具有光催化水还原产氢活性并且溶液pH值为9的环境中***光催化水还原产氢活性更高。
Claims (9)
2.权利要求1所述双核铱-铂配合物的制备方法,其特征在于,将铱(III)前驱体和六氟磷酸铂(Ⅱ)前驱体溶解于由二氯甲烷和三乙胺组成的混合溶液中,在避光环境下搅拌反应30±5分钟,随后加入碘化亚铜,于避光处加热回流搅拌反应100-140小时,反应结束后,冷却至室温再加入六氟磷酸铵水溶液继续搅拌反应30±5分钟,将反应产物萃取提纯,获得铱-铂双核配合物。
3.如权利要求2所述的制备方法,其特征在于,铱(Ⅲ)前驱体为Ir(tmfppy)2EPIP,其中,tmfppy为2-(4-(三氟甲基)苯基)吡啶,EPIP为2-[4-乙炔基苯基]-1H-咪唑并[4,5-f][1,10]邻菲罗啉。
4.如权利要求2或3所述的制备方法,其特征在于,六氟磷酸铂(Ⅱ)前驱体为[Pt(tBu3terpy)Cl]PF6。
5.如权利要求2或3所述的制备方法,其特征在于,铱(Ⅲ)前驱体和六氟磷酸铂(Ⅱ)前驱体的摩尔比为2:(3±0.5)。
6.如权利要求2或3所述的制备方法,其特征在于,二氯甲烷和三乙胺的摩尔比为674:(113±10),三乙胺与铱(Ⅲ)前驱体的摩尔比为105:(337±10)。
7.如权利要求2或3所述的制备方法,其特征在于,碘化亚铜在由二氯甲烷和三乙胺组成的混合溶液中的浓度为(0.625±0.1)mg/mL,碘化亚铜和铱(Ⅲ)前驱体的相对用量为(100±10)g碘化亚铜/1mol Ir(tmfppy)2EPIP,六氟磷酸铵水溶液和碘化亚铜的相对用量为(1±0.5)mL/mg,六氟磷酸铵水溶液的浓度为(0.5±0.1)mol/L。
8.如权利要求2或3所述的制备方法,其特征在于,萃取提纯方法为:将反应产物用二氯甲烷萃取、溶剂旋转蒸发干燥后,在硅胶柱中以体积比为(20±5):1的二氯甲烷和甲醇的混合液为洗脱剂进行色谱分离。
9.权利要求1所述双核铱-铂配合物在光催化还原水制氢中的应用。
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