CN105646551B - 三价金配合物及其在光催化还原水制氢中的应用 - Google Patents
三价金配合物及其在光催化还原水制氢中的应用 Download PDFInfo
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- 239000010931 gold Substances 0.000 title claims abstract description 50
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 title claims abstract description 41
- 229910052737 gold Inorganic materials 0.000 title claims abstract description 41
- 239000001257 hydrogen Substances 0.000 title claims abstract description 24
- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 24
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 20
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title claims abstract description 19
- 230000001699 photocatalysis Effects 0.000 title claims description 11
- 238000010531 catalytic reduction reaction Methods 0.000 title claims description 10
- 238000004519 manufacturing process Methods 0.000 title claims description 6
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims abstract description 42
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims abstract description 21
- 239000000460 chlorine Substances 0.000 claims abstract description 16
- UEXCJVNBTNXOEH-UHFFFAOYSA-N Ethynylbenzene Chemical group C#CC1=CC=CC=C1 UEXCJVNBTNXOEH-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000011259 mixed solution Substances 0.000 claims abstract description 10
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims abstract description 7
- 238000006243 chemical reaction Methods 0.000 claims abstract description 7
- 229910052801 chlorine Inorganic materials 0.000 claims abstract description 7
- 150000003222 pyridines Chemical class 0.000 claims abstract description 6
- 229910021595 Copper(I) iodide Inorganic materials 0.000 claims abstract description 5
- LSXDOTMGLUJQCM-UHFFFAOYSA-M copper(i) iodide Chemical compound I[Cu] LSXDOTMGLUJQCM-UHFFFAOYSA-M 0.000 claims abstract description 5
- 239000007795 chemical reaction product Substances 0.000 claims abstract description 4
- 238000002360 preparation method Methods 0.000 claims abstract description 4
- 239000000126 substance Substances 0.000 claims abstract description 4
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 12
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 12
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 8
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 6
- 239000003795 chemical substances by application Substances 0.000 claims description 6
- 239000003480 eluent Substances 0.000 claims description 6
- 238000001953 recrystallisation Methods 0.000 claims description 6
- 229910002027 silica gel Inorganic materials 0.000 claims description 6
- 239000000741 silica gel Substances 0.000 claims description 6
- 229960001866 silicon dioxide Drugs 0.000 claims description 6
- 239000002904 solvent Substances 0.000 claims description 6
- 238000007445 Chromatographic isolation Methods 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 4
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 claims description 3
- 238000000746 purification Methods 0.000 claims description 2
- 150000001335 aliphatic alkanes Chemical class 0.000 claims 1
- 239000003054 catalyst Substances 0.000 abstract description 6
- -1 ethynyl phenyl Chemical group 0.000 abstract description 2
- OTEKOJQFKOIXMU-UHFFFAOYSA-N 1,4-bis(trichloromethyl)benzene Chemical compound ClC(Cl)(Cl)C1=CC=C(C(Cl)(Cl)Cl)C=C1 OTEKOJQFKOIXMU-UHFFFAOYSA-N 0.000 abstract 1
- RHXQSMVSBYAGQV-UHFFFAOYSA-N 2-(4-tert-butylphenyl)pyridine Chemical class C1=CC(C(C)(C)C)=CC=C1C1=CC=CC=N1 RHXQSMVSBYAGQV-UHFFFAOYSA-N 0.000 abstract 1
- UJOBWOGCFQCDNV-UHFFFAOYSA-N 9H-carbazole Chemical class C1=CC=C2C3=CC=CC=C3NC2=C1 UJOBWOGCFQCDNV-UHFFFAOYSA-N 0.000 abstract 1
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 12
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 12
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 6
- 238000004458 analytical method Methods 0.000 description 5
- 125000003963 dichloro group Chemical group Cl* 0.000 description 5
- 150000002431 hydrogen Chemical class 0.000 description 5
- 238000005160 1H NMR spectroscopy Methods 0.000 description 4
- 238000005481 NMR spectroscopy Methods 0.000 description 4
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 4
- 229910017052 cobalt Inorganic materials 0.000 description 4
- 239000010941 cobalt Substances 0.000 description 4
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 4
- 238000002330 electrospray ionisation mass spectrometry Methods 0.000 description 4
- 230000001235 sensitizing effect Effects 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 150000004694 iodide salts Chemical class 0.000 description 3
- 238000006722 reduction reaction Methods 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 238000005868 electrolysis reaction Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 230000002829 reductive effect Effects 0.000 description 2
- 229910052703 rhodium Inorganic materials 0.000 description 2
- 239000010948 rhodium Substances 0.000 description 2
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 150000001345 alkine derivatives Chemical class 0.000 description 1
- 150000003851 azoles Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- LLVVIWYEOKVOFV-UHFFFAOYSA-L copper;diiodate Chemical compound [Cu+2].[O-]I(=O)=O.[O-]I(=O)=O LLVVIWYEOKVOFV-UHFFFAOYSA-L 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000011941 photocatalyst Substances 0.000 description 1
- 150000003233 pyrroles Chemical class 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 229910052724 xenon Inorganic materials 0.000 description 1
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 1
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- C07F1/00—Compounds containing elements of Groups 1 or 11 of the Periodic Table
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- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
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- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
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Abstract
本发明涉及一种三价金配合物，其化学通式为MAuL，其中，M为2,6‑二苯基吡啶或2,6‑双(4‑叔丁基苯基)吡啶，L为苯乙炔或3,6‑二‑叔丁基‑9‑(4‑乙炔基苯基)‑9H‑咔唑。制备方法：将氯金(III)前驱体和L溶解于由碘化亚铜、二氯甲烷和三乙胺组成的混合溶液中，室温下搅拌6‑12h，反应结束后，将反应产物提纯即得。本发明的三价金配合物具有可见光响应，是一种可以快速将水还原制备氢气的催化剂。
Description
技术领域
本发明涉及一种三价金配合物，属于光催化剂技术领域。
背景技术
当今社会的发展主要依赖于传统的化石能源，化石能源的应用推动了社会的发展，但资源却在日益耗尽；同时化石能源的无节制使用，造成了严重的环境污染和气候变化问题。开发利用可再生的新能源成为人类关注的重点。
太阳能具有普遍、无害、长久使用的特征，被视为21世纪最具发展潜力的清洁能源。氢气能否作为燃料使用，主要在于制氢工艺。在所有生产氢气的方式中，电解水可进行大规模生产制得氢气。然而，水分子中的氢原子结合得非常紧密，电解时需要消耗很大能量，比氢气本身燃烧产生的能量要多。光催化分解水制备氢气是利用光能使水分解，将太阳能转化为化学能。然而传统的半导体光催化剂具有吸收可见光能力差，催化速率缓慢的特征。寻找性能良好的光催化剂还原水制备氢气，可解决能源问题。鉴于以上情况，开发具有可见光响应，可以快速将水还原制备氢气的催化剂成为当下研究的热点。
发明内容
本发明的目的是解决现有技术的不足，提供一种三价金配合物，其具有可见光响应，是一种可以快速将水还原制备氢气的催化剂。
本发明的另一个目的还在于提供所述三价金配合物的制备方法。
技术方案
一种三价金配合物，其化学通式为MAuL，其中，M为2,6-二苯基吡啶或2,6-双(4-叔丁基苯基)吡啶，L为苯乙炔或3,6-二-叔丁基-9-(4-乙炔基苯基)-9H-咔唑。
作为优选，所述三价金配合物的通式中，M为2,6-双(4-叔丁基苯基)吡啶，L为苯乙炔。
所述三价金配合物的结构式有以下四种：
配合物1
配合物2
配合物3
配合物4
所述三价金配合物的制备方法：将氯金(III)前驱体和L溶解于由碘化亚铜、二氯甲烷和三乙胺组成的混合溶液中，室温下搅拌6-12h，反应结束后，将反应产物提纯得到三价金配合物；
所述氯金(III)前驱体为[Au(C^N^C)Cl]或[Au(tBuC^N^CtBu)Cl]。
所述氯金(III)前驱体和L的摩尔比为2:3-5。
所述混合溶液中，优选碘化亚铜、二氯甲烷和三乙胺的摩尔比为1:5460:14。
所述提纯方法为：将反应产物的溶剂旋干后在硅胶柱中以体积比为2:1的正己烷和二氯甲烷为洗脱剂进行色谱分离，再经过再结晶过程。
上述三价金配合物在光催化还原水制氢中的应用，本发明的三价金配合物克作为光敏剂参与光催化还原水制氢，现有技术中已经报道了某些光敏剂实现可见光催化还原水制备氢气的方法，本发明可以采用这些已有的光催化还原水的方法，只是本发明所述三价金配合物代替了现有技术的光敏剂。例如可以是，将三价金配合物、二氯三(2,2'-二吡啶)钴或者三(4,4'-二叔丁基-2,2'-二吡啶)铑、三乙醇胺(TEOA)，加入丙酮/水(v/v＝4:1)混合溶液中，用盐酸调pH至8.0，在可见光的照射下光催化还原水制备氢气。所述三价金配合物为光敏剂，TEOA为牺牲剂，二氯三(2,2'-二吡啶)钴或者三(4,4'-二叔丁基-2,2'-二吡啶)铑作为还原水催化剂。TEOA、二氯三(2,2'-二吡啶)钴或者三(4,4'-二叔丁基-2,2'-二吡啶)铑的用量均为现有技术。
有益效果：本发明提供了一系列三价金配合物，可以在丙酮和水的混合溶液中可见光催化还原制备氢气。
附图说明
图1为实施例1的三价金配合物的H谱图；
图2为实施例2的三价金配合物的H谱图；
图3为实施例3的三价金配合物的H谱图；
图4为实施例4的三价金配合物的H谱图；
图5为实施例1-4的三价金配合物用于光催化还原水制备氢气的氢气产出图。
具体实施方式
下面结合附图和实施例对本发明作进一步说明。
实施例1
将0.43mmol[Au(C^N^C)Cl]和0.1ml苯乙炔(摩尔比为1:2)溶解于由20mg碘化亚铜、35mL二氯甲烷和2mL三乙胺摩尔比为：1:5460:14组成的混合溶液中，室温下搅拌6h，反应结束后，将溶剂旋干后在硅胶柱中以体积比为2:1的正己烷和二氯甲烷为洗脱剂进行色谱分离，经过再结晶过程得到三价金配合物。
将三价金配合物进行核磁共振(H谱图见图1)，测得：1H NMR(DMSO,500MHz):δ8.16(1H,t,J＝8.0),7.98(2H,d,J＝8.0),7.90(4H,t,J＝6.0),7.54(2H,d,J＝7.3),7.41(4H,m),7.33(3H,m).元素分析，计算值:C25H16NAu:C,56.94；H,3.06；N,2.66.计算值:C,56.66；H,3.07；N,2.67.ESI-MS(甲醇):实测值:1076.83[2×M+Na]+.计算值:527.37。
实施例2
将0.52mmol[Au(C^N^C)Cl]和0.79ml 3,6-二-叔丁基-9-(4-乙炔基苯基)-9H-咔唑摩尔比为2:3溶解于由20mg碘化亚铜、35mL二氯甲烷和2mL三乙胺组成的混合溶液中，室温下搅拌8h，反应结束后，将溶剂旋干后在硅胶柱中以体积比为2:1的正己烷和二氯甲烷为洗脱剂进行色谱分离，经过再结晶过程得到三价金配合物。
将三价金配合物进行核磁共振(H谱图见图2)，测得：1H NMR(DMSO,500MHz):δ8.31(2H,s),8.20(1H,s),7.99(4H,t,J＝9.2),7.94(2H,s),7.80(2H,d,J＝7.6),7.62(2H,d,J＝7.9),7.52(2H,d,J＝7.9),7.46(2H,s),7.38(4H,m),1.44(16H,s).元素分析，计算值:C46H39NAu:C,68.74；H,5.02；N,1.74.实测值:C,68.48；H,5.14；N,1.67.ESIMS(甲醇):实测值:1632.08[2×M+Na]+.计算值:804.77。
实施例3
将0.1mL苯乙炔与0.43mmol[Au(C^N^C)Cl]、0.38mmol[Au(tBuC^N^CtBu)Cl](摩尔比为2:5)加入到由20mg碘化亚铜、35mL二氯甲烷和2mL三乙胺组成的混合溶液中，室温下搅拌6h，反应结束后，将溶剂旋干后在硅胶柱中以体积比为2:1的正己烷和二氯甲烷为洗脱剂进行色谱分离，经过再结晶过程得到三价金配合物。
将三价金配合物进行核磁共振(H谱图见图3)，测得：1H NMR(DMSO,500MHz):δ8.10(1H,t,J＝8.0),8.04(2H,d,J＝1.5),7.86(2H,d,J＝8.0),7.81(2H,d,J＝8.2),7.49(2H,d,J＝7.3),7.42(2H,t,J＝7.5),7.35(3H,m),1.34(18H,s).元素分析，计算值:C33H32NAu:C,61.97；H,5.04；N,2.19.实测值:C,61.86；H,5.12；N,2.26.ESI-MS(甲醇):实测值:1301.77[2×M+Na]+.计算值:639.58。
实施例4
将0.38mmol[Au(tBuC^N^CtBu)Cl]与0.57mmol 3,6-二-叔丁基-9-(4-乙炔基苯基)-9H-咔唑(摩尔比为2:3)加入到由20mg碘化亚铜、35mL二氯甲烷和2mL三乙胺组成的混合溶液中，室温下搅拌10h，反应结束后，将溶剂旋干后在硅胶柱中以体积比为2:1的正己烷和二氯甲烷为洗脱剂进行色谱分离，经过再结晶过程得到三价金配合物。
将三价金配合物进行核磁共振(H谱图见图4)，测得：1H NMR(DMSO,500MHz):δ8.31(2H,s),8.14(1H,t,J＝8.0),8.10(2H,s),7.92(2H,d,J＝8.0),7.85(2H,d,J＝8.2),7.76(2H,d,J＝8.2),7.68(2H,d,J＝8.3),7.52(2H,d,J＝8.5),7.39(4H,m),1.44(18H,s),1.37(16H,s).元素分析，计算值:C54H55NAu:C,70.81；H,6.16；N,1.53.实测值:C,70.75；H,6.19；N,1.48.ESI-MS(甲醇):实测值879.58[M-tBu+Na]+.计算值:916.98。
应用测试
将上述实施例制得的四种三价金配合物分别用于光催化还原水制备氢气，测试方法为：将40μmol三价金配合物加入到含有0.33mM二氯三(2,2'-二吡啶)钴，0.19M三乙醇胺的碱性丙酮/水(v/v＝4:1)的混合溶液中(100mL)，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5。
由图5可以看出，配合物1、2、3、4所在体系在光照24小时后生成氢气的量分别为788μmol、516μmol、1266μmol、1717μmol，可以看出配合物3的产氢量最高。
Claims (3)
1.一种三价金配合物的用途，其特征在于，三价金配合物用作光催化还原水制氢的催化剂；
三价金配合物的化学通式为MAuL，其中，M为2,6-二苯基吡啶或2,6-双(4-叔丁基苯基)吡啶，L为苯乙炔或3,6-二-叔丁基-9-(4-乙炔基苯基)-9H-咔唑，
上述三价金配合物的制备方法为，将氯金(III)前驱体和L溶解于由碘化亚铜、二氯甲烷和三乙胺组成的混合溶液中，室温下搅拌6-12h，反应结束后，将反应产物提纯得到三价金配合物；
所述氯金(III)前驱体为[Au(C^N^C)Cl]或[Au(tBuC^N^CtBu)Cl]；
所述氯金(III)前驱体和L的摩尔比为2:3-5；
所述混合溶液中，碘化亚铜、二氯甲烷和三乙胺的摩尔比为：1:5460:14。
2.如权利要求1所述的三价金配合物的用途，其特征在于，所述三价金配合物的通式中，M为2,6-双(4-叔丁基苯基)吡啶，L为苯乙炔。
3.如权利要求1所述的三价金配合物的用途，其特征在于，所述提纯方法为：将反应产物的溶剂旋干后在硅胶柱中以体积比为2:1的正己烷和二氯甲烷为洗脱剂进行色谱分离，再经过再结晶过程。
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