WO_3/g-C_3N_4异质结催化剂的制备及其氧化脱硫性能
|
摘要
以尿素和钨酸铵为原料采用浸渍法制备了金属氧化物三氧化钨(WO_3)与石墨相氮化碳(g-C_3N_4)异质结复合材料WO_3/g-C_3N_4。采用XRD、UV-vis、SEM、PL和XPS表征手段考察了催化剂的理化性质,发现WO_3与g-C_3N_4存在较好的相互作用和电子转移,保证了WO_3/g-C_3N_4本身所具有较高的氧化脱硫活性。以WO_3/g-C_3N_4作为催化剂,过氧化氢异丙苯为氧化剂,考察其光催化氧化脱硫性能,在反应温度80℃,O/S物质的量比为3.0的反应条件下,反应180 min,二苯并噻吩(DBT)转化率可以达到72.79%。通过游离基捕获实验,发现超氧自由基(·O_2~-)、电子(e~-)、羟基自由基(·OH)起到了促进反应速率的作用,并对该体系的反应机理进行了探讨。
Graphite phase carbon nitride( g-C_3N_4) and metal oxide tungsten trioxide( WO_3) heterojunction nanocomposites WO_3/g-C_3N_4 were prepared by roasting from urea and ammonium tungstate. The physical and chemical properties of the catalysts were investigated by means of XRD,UV-vis,SEM,PL and XPS. The characterization indicated that WO_3 and g-C_3N_4 interacted well in the catalysts,and electron transfer occurred between them,which ensured high oxidative desulfurization activity of WO_3/g-C_3N_4. Supported catalyst WO_3/gC_3N_4 was prepared using WO_3 as the support. Isopropyl peroxide was used as the oxidant to investigate the catalyst performance in oxidative desulfurization of the simulated oil. Under the reaction conditions of 80 ℃ and the content ratio of O/S at 3,a 72. 79% of dibenzothiophene( DBT) conversion could be achieved after180 min. It was fund that the superoxide free radicals(·O2-),electron( e-) and hydroxyl free radicals(·OH)promoted the reaction rate through free radical capture experiment and the reaction mechanism was proposed.
Graphite phase carbon nitride( g-C_3N_4) and metal oxide tungsten trioxide( WO_3) heterojunction nanocomposites WO_3/g-C_3N_4 were prepared by roasting from urea and ammonium tungstate. The physical and chemical properties of the catalysts were investigated by means of XRD,UV-vis,SEM,PL and XPS. The characterization indicated that WO_3 and g-C_3N_4 interacted well in the catalysts,and electron transfer occurred between them,which ensured high oxidative desulfurization activity of WO_3/g-C_3N_4. Supported catalyst WO_3/gC_3N_4 was prepared using WO_3 as the support. Isopropyl peroxide was used as the oxidant to investigate the catalyst performance in oxidative desulfurization of the simulated oil. Under the reaction conditions of 80 ℃ and the content ratio of O/S at 3,a 72. 79% of dibenzothiophene( DBT) conversion could be achieved after180 min. It was fund that the superoxide free radicals(·O2-),electron( e-) and hydroxyl free radicals(·OH)promoted the reaction rate through free radical capture experiment and the reaction mechanism was proposed.
引文
[1]蒋克望.石墨相氮化碳(g-C3N4)的复合改性及其光催化性能研究[D].南京:南京理工大学,2016.(JIANG Ke-wang. Composite modification and photocatalytic properties of graphite phase carbon nitride(g-C3N4)[D]. Nanjing:Nanjing University of Science and Technology,2016.)
[2]王鑫博,李秀萍,赵荣祥. EMIES/p-TsOH型低共熔溶剂的合成及其氧化脱硫性能的研究[J].燃料化学学报,2019,47(1):104-112.(WANG Xin-bo,LI Xiu-ping,ZHAO Rong-xiang. Synthesis of EMIES/p-TsOH low eutectic solvent and its oxidative desulfurization performance[J]. J Fuel Chem Technol,2019,47(1):104-112.)
[3]李秀萍,赵荣祥,邢鹏飞. NiWO4/g-C3N4的制备及其在离子液体中氧化脱硫性能的研究[J].燃料化学学报,2017,45(11):1340-1348.(LI Xiu-ping,ZHAO Rong-xiang,XING Peng-fei. Preparation of NiWO4/g-C3N4and its oxidative desulfurization performance in ionic liquid[J]. J Fuel Chem Technol,2017,45(11):1340-1348.)
[4] CHAN K,JUNG J L,JUN S B,KYUNGIL C,SANG H M. Hydrodesulfurization of DBT,4-MDBT,and 4,6-DMDBT on fluorinated CoMoS/Al2O3catalysts[J]. Appl Catal A:Gen,2000,200(1/2):233-242.
[5]刘优昌,王亮. g-C3N4/BiOBr异质结光催化剂的制备与可见光催化活性[J].燃料化学学报,2018,46(9):1146-1152.(LIU You-chang,WANG Liang. Preparation and visible light catalytic activity of g-C3N4/BiOBr heterojunction photocatalyst[J]. J Fuel Chem Technol,2018,46(9):1146-1152.)
[6] WANG X C,MAEDA K,THOMAS A,TAKANABE K,XIN G,CARLSSON J M,DOMEN K,ANTONIETTI M. A metal-free polymeric photocatalyst for hydrogen production from w ater under visible light[J]. Nat Mater,2009,8(1):76-80.
[7] KROKE E,SCHWARZ M,HORATH-BORDON E,KROLL P,NOLL B,NORMAN A D. Tri-s-triazine derivatives. Part I. From trichlorotri-triazine to graphitic C3N4structures[J]. New J Chem,2002,26(5):508-512.
[8]李秀萍,赵荣祥,苏建勋,艾东.磷钨酸功能化氮化碳的制备及其氧化脱硫研究[J].燃料化学学报,2015,43(7):870-875.(LI Xiu-ping,ZHAO Rong-xiang,SU Jian-xun,AI Dong. Preparation of functional nitride of phosphotungstic acid and its oxidative desulfurization[J]. J Fuel Chem Technol,2015,43(7):870-875.)
[9]闫俊萍,张中太,唐子龙,罗绍华.半导体基纳米复合材料光催化研究进展[J].无机材料学报,2003,18(5):980-988.(YAN Jun-ping,ZHANG Zhong-tai,TANG Zi-long,LUO Shao-hua. Progress in photocatalysis of semiconductor nanocomposites[J]. J Inorg Mater,2003,18(5):980-988.)
[10] TONG H X,CHEN Q Y,YIN Z L,HU H P,WU D X,YANG Y H. Preparation characterization and photo-catalytic behavior of WO3-TiO2catalysts w ith oxygen vacancies[J]. Trans Nonferrous Met Soc China,2009,19(6):1483-1488.
[11] SUN J X,YUAN Y P,QIU L G,JIANG X,XIE A J,SHEN Y H,ZHU J F. Fabrication of composite photocatalyst g-C3N4-ZnO and enhancement of photocatalytic activity under visible light[J]. Dalton Trans,2012,41(22):6756-6763.
[12] YAN H J,YANG H X. TiO2-g-C3N4composite materials for photocatalytic H2evolution under visible light irradiation[J]. J Alloys Compd,2011,509:L26-L29.
[13]邢鹏飞,李秀萍,贾宝军,赵荣祥. MoO3/g-C3N4催化剂的制备及其氧化脱除模拟油中的硫化物[J].化工进展,2016,35(12):3934-3941.(XING Peng-fei,LI Xiu-ping,JIA Bao-jun,ZHAO Rong-xiang. Preparation of MoO3/g-C3N4catalyst and its oxidation removal of sulfide in simulated oil[J]. Chem Ind Eng Prog,2016,35(12):3934-3941.)
[14] MIAO X L,SHEN X P,WU J J,JI Z Y,WANG J H,KONG L R,LIU MM,SONG C S. Fabrication of an all solid Z-scheme photocatalyst g-C3N4/GO/Ag Br w ith enhanced visible light photocatalytic activity[J]. Appl Catal A:Gen,2017,539:104-113.
[15] HUANG L Y,XU H,LI Y P,LI H M,CHENG X N,XIA J X,XU Y G,CAI G B. Visible-light-induced WO3/g-C3N4composites w ith enhanced photocatalytic activity[J]. Dalton Trans,2013,42(24):8606-8616.
[16] ZHAO Z G,MIYANUCHI M. Nanoporous-walled tungsten oxide nanotubes as highly active visible-light-driven photocatalysts[J]. Angew Chem-Int Ed,2008,47(37):7051-7055.
[17] KHALID N R,AHMED E,HONG Z L,AHMAD M. Synthesis and photocatalytic properties of visible light responsive La/TiO2-graphene composites[J]. Appl Surf Sci,2012,263:254-259.
[18] AMOOZADEH A,RAHMANI S. Nano-WO3-supported sulfonic acid:New efficient and high reusable heterogeneous nanocatalyst[J]. J Mol Catal A:Chem,2015,396:96-107.
[19]桂明生,王鹏飞,袁东,杨易坤. Bi2WO6/g-C3N4复合型催化剂的制备及其可见光光催化性能[J].无机化学学报,2013,29(10):2057-2064.(GUI Ming-sheng,WANG Peng-fei,YUAN Dong,YANG Yi-kun. Preparation of Bi2WO6/g-C3N4composite catalyst and its visible photocatalytic performance[J]. J Inorg Chem,2013,29(10):2057-2064.)
[20] GAO Y,JIANG P,LIU D F,YUAN H J,YAN X Q,ZHOU Z P,WANG J X,SONG L,LIU L F,ZWOU W Y,WANG C Y,XIE S S. Synthesis,characterization and self-assembly of silver nanow ires[J]. Chem Phys Lett,2003,380(1):146-149.
[21] CHAI B,PENG T,MAO J,LI K,ZAN L. Graphitic carbon nitride(g-C3N4)-Pt-TiO2nanocomposite as an efficient photocatalyst for hydrogen production under visible light irradiation[J]. Phys Chem Chem Phys,2012,14(48):16745-16752.
[22] YANG Y X,GUO Y N,LIU F Y,YUAN X,GUO Y H,ZHANG S Q,GUO W,HUO MX. Preparation and enhanced visible-light photocatalytic activity of silver deposited graphitic carbon nitride plasmonic photocatalyst[J]. Appl Catal B:Environ,2013,142/143:828-837.
[23] ERDEMB,HUNSICKER R A,SIMMONS G W,SUDOL E D,DIMONIE V L,El-AASSER MS. XPS and FT-IR surface characterization of TiO2particles used polymer encapsulation[J]. Langmuir,2001,17(9):2664-2669.
[24] XUN S H,ZHU W S,CHANG Y H,LI H P,ZHANG M,JIANG W,ZHENG D,QIN Y J,LI H M. Synthesis of supported SiW12O40-based ionic liquid catalyst induced solvent-free oxidative deep-desulfurization of fuels[J]. Chem Eng J,2016,288:608-617.
[25] CHEN K,ZHANG X M,YANG X F,JIAO MG,ZHOU Z,ZHANG MH,WANG D H,BU X H. Electronic structure of heterojunction MoO2/g-C3N4catalyst for oxidative desulfurization[J]. Appl Catal B:Environ,2018,238:263-273.
[26]张黎明,吴磊,邵云,李莲. Cu-g-C3N4/WO3可见光下降解四环素的性能研究[J].人工晶体学报,2018,47(6):1128-1135.(ZHANG Li-ming,WU Lei,SHAO Yun,LI Lei. Study on the properties of Cu-g-C3N4/WO3degraded tetracycline[J]. J Synth Cryst,2018,47(6):1128-1135.)
[27]王丽,赵辉. WO3/N-TiO2异质节可见光催化降解亚甲基蓝[J].工业水处理,2016,36(11):78-81.(WANG Li,ZHAO Hui. Visible light catalytic degradation of methylene blue by WO3/N TiO2heterogeneous[J]. Ind Water Treat,2016,36(11):78-81.)
[28] LI X F,ZHANG J,SHEN L H,MA Y M,LEI W W,CUI Q L,ZOU G T. Preparation and characterization of graphitic carbon nitride through pyrolysis of melamine[J]. Appl Phys A:Mater,2009,94(2):387-392.
[29] LIU H,JIN Z T,XU Z Z,ZHANG Z,AO D. Fabrication of ZnIn2S4-g-C3N4sheet-on-sheet nanocomposites for efficient visible-light photocatalytic H2-evolution and degradation of organic pollutants[J]. RSC Adv,2015,5(119):97951-97961.
[30] KATSUMATA H,TACHI Y,SUZUKI T,KANECO S. Z-scheme photocatalytic hydrogen production over WO3/g-C3N4composite photocatalysts[J]. RSC Adv,2014,4(41):21405-21409.
[31] MA S S,XUE J J,ZHOU Y M,ZHANG Z W. Facile fabrication of mpg-C3N4/TiO2heterojunction photocatalyst w ith enhanced visible light photoactivity tow ard organic pollutant degradation[J]. RSC Adv,2015,5(80):64976-64982.
[32] XIAO X,ZHONG H,ZHENG C X,LU ML,ZUO X X,NAN J M. Deep oxidative desulfurization of dibenzothiophene using a flower-like WO3·H2O catalyst in an organic biphasic system[J]. Chem Eng J,2016,304:908-916.
[33]卞振锋,阮大明,李和兴. Pt负载对TiO2光催化氧化还原的影响[J].中国科技论文,2016,11(18):2091-2095.(BIAN Zhen-feng,RUAN Da-ming,LI He-xing. Effect of Pt loading on photocatalytic REDOX of TiO2[J]. Chin J Sci Technol,2016,11(18):2091-2095.)
[2]王鑫博,李秀萍,赵荣祥. EMIES/p-TsOH型低共熔溶剂的合成及其氧化脱硫性能的研究[J].燃料化学学报,2019,47(1):104-112.(WANG Xin-bo,LI Xiu-ping,ZHAO Rong-xiang. Synthesis of EMIES/p-TsOH low eutectic solvent and its oxidative desulfurization performance[J]. J Fuel Chem Technol,2019,47(1):104-112.)
[3]李秀萍,赵荣祥,邢鹏飞. NiWO4/g-C3N4的制备及其在离子液体中氧化脱硫性能的研究[J].燃料化学学报,2017,45(11):1340-1348.(LI Xiu-ping,ZHAO Rong-xiang,XING Peng-fei. Preparation of NiWO4/g-C3N4and its oxidative desulfurization performance in ionic liquid[J]. J Fuel Chem Technol,2017,45(11):1340-1348.)
[4] CHAN K,JUNG J L,JUN S B,KYUNGIL C,SANG H M. Hydrodesulfurization of DBT,4-MDBT,and 4,6-DMDBT on fluorinated CoMoS/Al2O3catalysts[J]. Appl Catal A:Gen,2000,200(1/2):233-242.
[5]刘优昌,王亮. g-C3N4/BiOBr异质结光催化剂的制备与可见光催化活性[J].燃料化学学报,2018,46(9):1146-1152.(LIU You-chang,WANG Liang. Preparation and visible light catalytic activity of g-C3N4/BiOBr heterojunction photocatalyst[J]. J Fuel Chem Technol,2018,46(9):1146-1152.)
[6] WANG X C,MAEDA K,THOMAS A,TAKANABE K,XIN G,CARLSSON J M,DOMEN K,ANTONIETTI M. A metal-free polymeric photocatalyst for hydrogen production from w ater under visible light[J]. Nat Mater,2009,8(1):76-80.
[7] KROKE E,SCHWARZ M,HORATH-BORDON E,KROLL P,NOLL B,NORMAN A D. Tri-s-triazine derivatives. Part I. From trichlorotri-triazine to graphitic C3N4structures[J]. New J Chem,2002,26(5):508-512.
[8]李秀萍,赵荣祥,苏建勋,艾东.磷钨酸功能化氮化碳的制备及其氧化脱硫研究[J].燃料化学学报,2015,43(7):870-875.(LI Xiu-ping,ZHAO Rong-xiang,SU Jian-xun,AI Dong. Preparation of functional nitride of phosphotungstic acid and its oxidative desulfurization[J]. J Fuel Chem Technol,2015,43(7):870-875.)
[9]闫俊萍,张中太,唐子龙,罗绍华.半导体基纳米复合材料光催化研究进展[J].无机材料学报,2003,18(5):980-988.(YAN Jun-ping,ZHANG Zhong-tai,TANG Zi-long,LUO Shao-hua. Progress in photocatalysis of semiconductor nanocomposites[J]. J Inorg Mater,2003,18(5):980-988.)
[10] TONG H X,CHEN Q Y,YIN Z L,HU H P,WU D X,YANG Y H. Preparation characterization and photo-catalytic behavior of WO3-TiO2catalysts w ith oxygen vacancies[J]. Trans Nonferrous Met Soc China,2009,19(6):1483-1488.
[11] SUN J X,YUAN Y P,QIU L G,JIANG X,XIE A J,SHEN Y H,ZHU J F. Fabrication of composite photocatalyst g-C3N4-ZnO and enhancement of photocatalytic activity under visible light[J]. Dalton Trans,2012,41(22):6756-6763.
[12] YAN H J,YANG H X. TiO2-g-C3N4composite materials for photocatalytic H2evolution under visible light irradiation[J]. J Alloys Compd,2011,509:L26-L29.
[13]邢鹏飞,李秀萍,贾宝军,赵荣祥. MoO3/g-C3N4催化剂的制备及其氧化脱除模拟油中的硫化物[J].化工进展,2016,35(12):3934-3941.(XING Peng-fei,LI Xiu-ping,JIA Bao-jun,ZHAO Rong-xiang. Preparation of MoO3/g-C3N4catalyst and its oxidation removal of sulfide in simulated oil[J]. Chem Ind Eng Prog,2016,35(12):3934-3941.)
[14] MIAO X L,SHEN X P,WU J J,JI Z Y,WANG J H,KONG L R,LIU MM,SONG C S. Fabrication of an all solid Z-scheme photocatalyst g-C3N4/GO/Ag Br w ith enhanced visible light photocatalytic activity[J]. Appl Catal A:Gen,2017,539:104-113.
[15] HUANG L Y,XU H,LI Y P,LI H M,CHENG X N,XIA J X,XU Y G,CAI G B. Visible-light-induced WO3/g-C3N4composites w ith enhanced photocatalytic activity[J]. Dalton Trans,2013,42(24):8606-8616.
[16] ZHAO Z G,MIYANUCHI M. Nanoporous-walled tungsten oxide nanotubes as highly active visible-light-driven photocatalysts[J]. Angew Chem-Int Ed,2008,47(37):7051-7055.
[17] KHALID N R,AHMED E,HONG Z L,AHMAD M. Synthesis and photocatalytic properties of visible light responsive La/TiO2-graphene composites[J]. Appl Surf Sci,2012,263:254-259.
[18] AMOOZADEH A,RAHMANI S. Nano-WO3-supported sulfonic acid:New efficient and high reusable heterogeneous nanocatalyst[J]. J Mol Catal A:Chem,2015,396:96-107.
[19]桂明生,王鹏飞,袁东,杨易坤. Bi2WO6/g-C3N4复合型催化剂的制备及其可见光光催化性能[J].无机化学学报,2013,29(10):2057-2064.(GUI Ming-sheng,WANG Peng-fei,YUAN Dong,YANG Yi-kun. Preparation of Bi2WO6/g-C3N4composite catalyst and its visible photocatalytic performance[J]. J Inorg Chem,2013,29(10):2057-2064.)
[20] GAO Y,JIANG P,LIU D F,YUAN H J,YAN X Q,ZHOU Z P,WANG J X,SONG L,LIU L F,ZWOU W Y,WANG C Y,XIE S S. Synthesis,characterization and self-assembly of silver nanow ires[J]. Chem Phys Lett,2003,380(1):146-149.
[21] CHAI B,PENG T,MAO J,LI K,ZAN L. Graphitic carbon nitride(g-C3N4)-Pt-TiO2nanocomposite as an efficient photocatalyst for hydrogen production under visible light irradiation[J]. Phys Chem Chem Phys,2012,14(48):16745-16752.
[22] YANG Y X,GUO Y N,LIU F Y,YUAN X,GUO Y H,ZHANG S Q,GUO W,HUO MX. Preparation and enhanced visible-light photocatalytic activity of silver deposited graphitic carbon nitride plasmonic photocatalyst[J]. Appl Catal B:Environ,2013,142/143:828-837.
[23] ERDEMB,HUNSICKER R A,SIMMONS G W,SUDOL E D,DIMONIE V L,El-AASSER MS. XPS and FT-IR surface characterization of TiO2particles used polymer encapsulation[J]. Langmuir,2001,17(9):2664-2669.
[24] XUN S H,ZHU W S,CHANG Y H,LI H P,ZHANG M,JIANG W,ZHENG D,QIN Y J,LI H M. Synthesis of supported SiW12O40-based ionic liquid catalyst induced solvent-free oxidative deep-desulfurization of fuels[J]. Chem Eng J,2016,288:608-617.
[25] CHEN K,ZHANG X M,YANG X F,JIAO MG,ZHOU Z,ZHANG MH,WANG D H,BU X H. Electronic structure of heterojunction MoO2/g-C3N4catalyst for oxidative desulfurization[J]. Appl Catal B:Environ,2018,238:263-273.
[26]张黎明,吴磊,邵云,李莲. Cu-g-C3N4/WO3可见光下降解四环素的性能研究[J].人工晶体学报,2018,47(6):1128-1135.(ZHANG Li-ming,WU Lei,SHAO Yun,LI Lei. Study on the properties of Cu-g-C3N4/WO3degraded tetracycline[J]. J Synth Cryst,2018,47(6):1128-1135.)
[27]王丽,赵辉. WO3/N-TiO2异质节可见光催化降解亚甲基蓝[J].工业水处理,2016,36(11):78-81.(WANG Li,ZHAO Hui. Visible light catalytic degradation of methylene blue by WO3/N TiO2heterogeneous[J]. Ind Water Treat,2016,36(11):78-81.)
[28] LI X F,ZHANG J,SHEN L H,MA Y M,LEI W W,CUI Q L,ZOU G T. Preparation and characterization of graphitic carbon nitride through pyrolysis of melamine[J]. Appl Phys A:Mater,2009,94(2):387-392.
[29] LIU H,JIN Z T,XU Z Z,ZHANG Z,AO D. Fabrication of ZnIn2S4-g-C3N4sheet-on-sheet nanocomposites for efficient visible-light photocatalytic H2-evolution and degradation of organic pollutants[J]. RSC Adv,2015,5(119):97951-97961.
[30] KATSUMATA H,TACHI Y,SUZUKI T,KANECO S. Z-scheme photocatalytic hydrogen production over WO3/g-C3N4composite photocatalysts[J]. RSC Adv,2014,4(41):21405-21409.
[31] MA S S,XUE J J,ZHOU Y M,ZHANG Z W. Facile fabrication of mpg-C3N4/TiO2heterojunction photocatalyst w ith enhanced visible light photoactivity tow ard organic pollutant degradation[J]. RSC Adv,2015,5(80):64976-64982.
[32] XIAO X,ZHONG H,ZHENG C X,LU ML,ZUO X X,NAN J M. Deep oxidative desulfurization of dibenzothiophene using a flower-like WO3·H2O catalyst in an organic biphasic system[J]. Chem Eng J,2016,304:908-916.
[33]卞振锋,阮大明,李和兴. Pt负载对TiO2光催化氧化还原的影响[J].中国科技论文,2016,11(18):2091-2095.(BIAN Zhen-feng,RUAN Da-ming,LI He-xing. Effect of Pt loading on photocatalytic REDOX of TiO2[J]. Chin J Sci Technol,2016,11(18):2091-2095.)