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
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- 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
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- 238000004519 manufacturing process Methods 0.000 claims description 8
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- 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
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- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 9
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- 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
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- 241000282414 Homo sapiens Species 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系统中的光吸收组分和光催化位点连接起来，使得光催化产氢系统简化为由单个分子组成的超分子光催化产氢系统，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系统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)的溶液环境中该系统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的环境中系统光催化水还原产氢活性更高。
Claims (9)
1.一种双核铱-铂配合物，其特征在于：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，双核铱-铂配合物的结构式如下：
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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