石墨烯助剂与Ni(Ⅱ)活性位点协同增强TiO_2制氢性能
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摘要
采用水热法和低温浸渍法制备了电子助剂还原石墨烯(rGO)和界面活性位点Ni(Ⅱ)共修饰的高效TiO_2光催化剂(简称Ni(Ⅱ)/TiO_2-rGO)。制氢性能测试结果表明:相比于TiO_2和单独还原石墨烯复合的TiO_2,经还原石墨烯与Ni(Ⅱ)协同修饰后的TiO_2表现出更高的光催化制氢性能。其中,Ni(Ⅱ)/TiO_2-rGO(0.1 mol·L-1)具有最高制氢性能,制氢速率达到77.0μmol·h-1,分别是TiO_2(16.4μmol·h-1)和TiO_2-rGO(28.0μmol·h-1)的4.70倍和2.75倍。还原石墨烯助剂与Ni(Ⅱ)活性位点协同增强制氢性能的原理是:还原石墨烯作为电子助剂可以快速捕获和传输电子,Ni(Ⅱ)作为界面活性位点可以从溶液中捕获H+,提高界面反应速率,2种助剂协同作用加快了TiO_2上的光生电子-空穴对的有效分离。
Highly efficient TiO_2photocatalysts co-modified by reduced graphene oxide(rGO) as electron-transfer mediator and Ni( Ⅱ)as interfacial catalytic active-sites(referred to as Ni( Ⅱ)/TiO_2-rGO) were synthesized via a twostep process including the initial hydrothermal method of rGO on the TiO_2surface and the following lowtemperature impregnation method of Ni(Ⅱ)on the rGO. Photocatalytic experimental results indicated that all resulted Ni(Ⅱ)/TiO_2-rGO photocatalysts exhibited obviously high H2-production performance. The highest H2-production rate of the resultant Ni(Ⅱ)/TiO_2-rGO(0.1 mol·L-1) reached 77.0 μmol·h-1, while this value was higher than that of the TiO_2(16.4 μmol·h-1) and TiO_2-rGO(28.0 μmol·h-1) by a factor of 4.70 and 2.75, respectively. On the basis of the experimental results,a synergistic effect mechanism of rGO and Ni(Ⅱ)bi-cocatalysts was proposed to account for its enhanced H2-production performance, namely, rGO functions as an electron-transfer mediator to rapidly capture and transfer the photogenerated electron from TiO_2surface, while the Ni( Ⅱ)cocatalyst serves as an effectively active site for the following reduction.
Highly efficient TiO_2photocatalysts co-modified by reduced graphene oxide(rGO) as electron-transfer mediator and Ni( Ⅱ)as interfacial catalytic active-sites(referred to as Ni( Ⅱ)/TiO_2-rGO) were synthesized via a twostep process including the initial hydrothermal method of rGO on the TiO_2surface and the following lowtemperature impregnation method of Ni(Ⅱ)on the rGO. Photocatalytic experimental results indicated that all resulted Ni(Ⅱ)/TiO_2-rGO photocatalysts exhibited obviously high H2-production performance. The highest H2-production rate of the resultant Ni(Ⅱ)/TiO_2-rGO(0.1 mol·L-1) reached 77.0 μmol·h-1, while this value was higher than that of the TiO_2(16.4 μmol·h-1) and TiO_2-rGO(28.0 μmol·h-1) by a factor of 4.70 and 2.75, respectively. On the basis of the experimental results,a synergistic effect mechanism of rGO and Ni(Ⅱ)bi-cocatalysts was proposed to account for its enhanced H2-production performance, namely, rGO functions as an electron-transfer mediator to rapidly capture and transfer the photogenerated electron from TiO_2surface, while the Ni( Ⅱ)cocatalyst serves as an effectively active site for the following reduction.
引文
[1]Preethi V,Kanmani S.Mater.Sci.Semicond.Process.,2013,16:561-575
[2]Ismail A A,Bahnemann D W.Sol.Energy Mater.Sol.Cells,2014,128:85-101
[3]LI Cao-Long(李曹龙),WANG Fei(王飞),TANG Yuan-Yuan(唐媛媛),et al.Chinese J.Inorg.Chem.(无机化学学报),2016,32:1375-1382
[4]YANG Xu(杨旭),LI Xiao-Long(李小龙),HU Cai-Hua(胡彩花),et al.Chinese J.Inorg.Chem.(无机化学学报),2015,31:2167-2173
[5]Ni M,Leung M K H,Leung D Y C,et al.Renewable Sustainable Energy Rev.,2007,11:401-425
[6]Wang P,Wang J,Ming T,et al.ACS Appl.Mater.Interfaces,2013,5:2924-2923
[7]Le T T,Akhtar M S,Park D M,et al.Appl.Catal.,B,2012,111-112:397-401
[8]Han C,Wang Y,Lei Y,et al.Nano Res.,2014,8:1199-1209
[9]Li K,Chai B,Peng T,et al.ACS Catal.,2013,3:170-177
[10]Tanaka A,Sakaguchi S,Hashimoto K,et al.ACS Catal.,2013,3:79-85
[11]Xiang Q,Yu J,Jaroniec M.J.Am.Chem.Soc.,2012,134:6575-6578
[12]GUO Dan(郭丹),WANG Ping(王苹),ZHENG Qi-Ying(郑琪颖),et al.J.Inorg.Mater.(无机材料学报),2014,29:1193-1198
[13]Wang F,Zheng M,Zhu C,et al.Nanotechnology,2015,26:345402-345410
[14]Chen D,Zou L,Li S,et al.Sci.Rep.,2016,6:20335-20343
[15]Wang P,Wang J,Wang X,et al.Appl.Catal.,B:Environ.,2013,132-133:452-459
[16]Zhang X Y,Li H P,Cui X L,et al.J.Mater.Chem.,2010,20:2801-2806
[17]Li Z,Xiao J D,Jiang H,L.ACS Catal.,2016,6:5359-5365
[18]Indra A,Menezes P W,Kailasam K,et al.Chem.Commun.,2016,52:104-111
[19]Yu H,Tian J,Chen F,et al.Sci.Rep.,2015,5:13083-13094
[20]Yu H,Huang X,Wang P,et al.J.Phys.Chem.C,2016,120:3722-3730
[21]Wang P,Lu Y,Wang X,et al.Appl.Surf.Sci.,2017,391:259-266
[22]WANG Ming-Fang(王明芳),WANG Ping(王苹),XU ShunQiu(徐顺秋),et al.Chinese J.Inorg.Chem.(无机化学学报),2015,31:1981-1986
[23]Wang P,Xia Y,Wu P,et al.J.Phys.Chem.C,2014,118:8891-8898
[24]Yu J,Hai Y,Cheng B.J.Phys.Chem.C,2011,115:4953-4958
[25]Wang J,Xu F,Jin H,et al.Adv.Mater.,2017,DOI:10.1002/adma.201605838
[2]Ismail A A,Bahnemann D W.Sol.Energy Mater.Sol.Cells,2014,128:85-101
[3]LI Cao-Long(李曹龙),WANG Fei(王飞),TANG Yuan-Yuan(唐媛媛),et al.Chinese J.Inorg.Chem.(无机化学学报),2016,32:1375-1382
[4]YANG Xu(杨旭),LI Xiao-Long(李小龙),HU Cai-Hua(胡彩花),et al.Chinese J.Inorg.Chem.(无机化学学报),2015,31:2167-2173
[5]Ni M,Leung M K H,Leung D Y C,et al.Renewable Sustainable Energy Rev.,2007,11:401-425
[6]Wang P,Wang J,Ming T,et al.ACS Appl.Mater.Interfaces,2013,5:2924-2923
[7]Le T T,Akhtar M S,Park D M,et al.Appl.Catal.,B,2012,111-112:397-401
[8]Han C,Wang Y,Lei Y,et al.Nano Res.,2014,8:1199-1209
[9]Li K,Chai B,Peng T,et al.ACS Catal.,2013,3:170-177
[10]Tanaka A,Sakaguchi S,Hashimoto K,et al.ACS Catal.,2013,3:79-85
[11]Xiang Q,Yu J,Jaroniec M.J.Am.Chem.Soc.,2012,134:6575-6578
[12]GUO Dan(郭丹),WANG Ping(王苹),ZHENG Qi-Ying(郑琪颖),et al.J.Inorg.Mater.(无机材料学报),2014,29:1193-1198
[13]Wang F,Zheng M,Zhu C,et al.Nanotechnology,2015,26:345402-345410
[14]Chen D,Zou L,Li S,et al.Sci.Rep.,2016,6:20335-20343
[15]Wang P,Wang J,Wang X,et al.Appl.Catal.,B:Environ.,2013,132-133:452-459
[16]Zhang X Y,Li H P,Cui X L,et al.J.Mater.Chem.,2010,20:2801-2806
[17]Li Z,Xiao J D,Jiang H,L.ACS Catal.,2016,6:5359-5365
[18]Indra A,Menezes P W,Kailasam K,et al.Chem.Commun.,2016,52:104-111
[19]Yu H,Tian J,Chen F,et al.Sci.Rep.,2015,5:13083-13094
[20]Yu H,Huang X,Wang P,et al.J.Phys.Chem.C,2016,120:3722-3730
[21]Wang P,Lu Y,Wang X,et al.Appl.Surf.Sci.,2017,391:259-266
[22]WANG Ming-Fang(王明芳),WANG Ping(王苹),XU ShunQiu(徐顺秋),et al.Chinese J.Inorg.Chem.(无机化学学报),2015,31:1981-1986
[23]Wang P,Xia Y,Wu P,et al.J.Phys.Chem.C,2014,118:8891-8898
[24]Yu J,Hai Y,Cheng B.J.Phys.Chem.C,2011,115:4953-4958
[25]Wang J,Xu F,Jin H,et al.Adv.Mater.,2017,DOI:10.1002/adma.201605838