N原子杂化石墨烯高效活化过一硫酸盐降解RBk5染料废水
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摘要
过硫酸盐高级氧化技术使用过程中,活化剂的大量流失与其环境二次危害是影响该技术应用的主要限制因素.针对这一问题本研究采用改进的Hummers法结合水热法制备环境友好型的N原子掺杂石墨烯作为催化剂,活化过一硫酸盐(PMS)产生硫酸根自由基(SO4-·)和羟基自由基(·OH)降解活性黑5(RBk5)染料.利用傅立叶红外光谱,X-射线光电子能谱,拉曼光谱和透射电子显微镜对N原子掺杂石墨烯进行表征.对催化剂催化性能进行研究,考察了初始p H、催化剂投加量和PMS投加量等因素对降解过程的影响.结果表明,N元素掺杂能够有效提升石墨烯材料的PMS催化活性,且活性受N掺杂比例影响较大;废水的初始p H对降解效率无明显影响.催化剂投加量为1. 5 g·L-1,PMS投加量为0. 3 g·L-1的条件下,反应25min后RBk5染料废水的降解率可达到99%以上,反应过程符合一级反应动力学.自由基猝灭实验显示,N掺杂石墨烯/PMS体系降解RBk5为表面反应,SO4-·和·OH为降解RBk5的主要自由基.循环实验证明催化剂稳定性能良好.
The large loss of catalysts and secondary pollution problems are bottlenecks for the utilization of persulfate advanced oxidation processes. Thus,a modified Hummers method combined with a hydrothermal method was used to prepare N-doped graphene as a catalyst for peroxymonosulfate( PMS) activation. The produced sulfate radical( SO4-·) and hydroxyl radical(·OH) were able to degrade RBk5. N-doped graphene was characterized by Fourier transform infrared, X-ray photoelectron spectroscopy, Raman spectroscopy,and transmission electron microscopy. The influences of vital parameters( i. e.,initial p H,catalyst dosage,and PMS dosage) on RBk5 removal were investigated systematically to examine the catalytic performance. The results showed that the N element doping can effectively improve the catalytic activity of graphene,and the activity is greatly affected by the N doping ratio. The initial p H of the wastewater had no significant effect on the degradation efficiency. Under the condition of 1. 5 g·L-1 catalyst dosage and 0. 3 g·L-1 PMS dosage,the removal rate of RBk5 dye reached 99% after 25 min of reaction. The reaction process accorded with first-order reaction kinetics. Radical quenching experiments were done and indicated that the degradation of RBk5 in N-doped graphene/PMS systems was a surface reaction,and SO4-· and ·OH were identified as the main radical species. The catalyst exhibited excellent stability over five successive degradation cycles.
The large loss of catalysts and secondary pollution problems are bottlenecks for the utilization of persulfate advanced oxidation processes. Thus,a modified Hummers method combined with a hydrothermal method was used to prepare N-doped graphene as a catalyst for peroxymonosulfate( PMS) activation. The produced sulfate radical( SO4-·) and hydroxyl radical(·OH) were able to degrade RBk5. N-doped graphene was characterized by Fourier transform infrared, X-ray photoelectron spectroscopy, Raman spectroscopy,and transmission electron microscopy. The influences of vital parameters( i. e.,initial p H,catalyst dosage,and PMS dosage) on RBk5 removal were investigated systematically to examine the catalytic performance. The results showed that the N element doping can effectively improve the catalytic activity of graphene,and the activity is greatly affected by the N doping ratio. The initial p H of the wastewater had no significant effect on the degradation efficiency. Under the condition of 1. 5 g·L-1 catalyst dosage and 0. 3 g·L-1 PMS dosage,the removal rate of RBk5 dye reached 99% after 25 min of reaction. The reaction process accorded with first-order reaction kinetics. Radical quenching experiments were done and indicated that the degradation of RBk5 in N-doped graphene/PMS systems was a surface reaction,and SO4-· and ·OH were identified as the main radical species. The catalyst exhibited excellent stability over five successive degradation cycles.
引文
[1] Liang C J,Wang Z S,Mohanty N. Influences of carbonate and chloride ions on persulfate oxidation of trichloroethylene at 20℃[J]. Science of the Total Environment,2006,370(2-3):271-277.
[2] Khan N E,Adewuyi Y G. Absorption and oxidation of nitric oxide(NO)by aqueous solutions of sodium persulfate in a bubble column reactor[J]. Industrial&Engineering Chemistry Research,2010,49(18):8749-8760.
[3]刘琰,孙德智.高级氧化技术处理染料废水的研究进展[J].工业水处理,2006,26(6):1-5.Liu Y,Sun D Z. Study progress of dye wastewater treatment by advanced oxidation processes[J]. Industrial Water Treatment,2006,26(6):1-5.
[4] Zhou G L,Sun H Q,Wang S B,et al. Titanate supported cobalt catalysts for photochemical oxidation of phenol under visible light irradiations[J]. Separation and Purification Technology,2011,80(3):626-634.
[5] Tan C Q,Gao N Y,Deng Y,et al. Heat-activated persulfate oxidation of diuron in water[J]. Chemical Engineering Journal,2012,203:294-300.
[6] Tan C Q,Gao N Y,Yang D,et al. Degradation of antipyrine by heat activated persulfate[J]. Separation and Purification Technology,2013,109:122-128.
[7] Shukla P,Sun H Q,Wang S B,et al. Nanosized Co3O4/SiO2for heterogeneous oxidation of phenolic contaminants in waste water[J]. Separation and Purification Technology,2011,77(2):230-236.
[8] Liang H W,Sun H Q,Patel A,et al. Excellent performance of mesoporous Co3O4/MnO2nanoparticles in heterogeneous activation of peroxymonosulfate for phenol degradation in aqueous solutions[J]. Applied Catalysis B:Environmental,2012,127:330-335.
[9] Kuila T,Bose S,Mishra A K,et al. Chemical functionalization of graphene and its applications[J]. Progress in Materials Science,2012,57(7):1061-1105.
[10] Zhang L P,Xia Z H. Mechanisms of oxygen reduction reaction on nitrogen-doped graphene for fuel cells[J]. The Journal of Physical Chemistry C,2011,115(22):11170-11176.
[11] Yao Y J,Xu C,Yu S M,et al. Facile synthesis of Mn3O4-reduced graphene oxide hybrids for catalytic decomposition of aqueous organics[J]. Industrial&Engineering Chemistry Research,2013,52(10):3637-3645.
[12]周雪君,时鹏辉,姚伟峰.掺氮石墨烯的制备及其催化性能研究[J].上海电力学院学报,2016,32(4):333-338.Zhou X J,Shi P H,Yao W F. Preparation and research of nitrogen-modified graphene[J]. Journal of Shanghai University of Electric Power,2016,32(4):333-338.
[13] Perera S D,Mariano R G,Vu K,et al. Hydrothermal synthesis of graphene-TiO2nanotube composites with enhanced photocatalytic activity[J]. ACS Catalysis,2012,2(6):949-956.
[14]吴丽颖,王炳煌,张圆春,等.凝胶球负载零价铁活化过硫酸盐降解偶氮染料废水[J].化工进展,2017,36(6):2318-2324.Wu L Y,Wang B H,Zhang Y C,et al. Degradation of reactive black5(RBk5)by gelatin balls loading iron activating sodium persulfate[J]. Chemical Industry and Engineering Progress,2017,36(6):2318-2324.
[15] Duan X G,O'donnell K,Sun H Q,et al. Sulfur and nitrogen Co-doped graphene for metal-free catalytic oxidation reactions[J]. Small,2015,11(25):3036-3044.
[16] Sun L,Wang L,Tian C G,et al. Nitrogen-doped graphene with high nitrogen level via a one-step hydrothermal reaction of graphene oxide with urea for superior capacitive energy storage[J]. RSC Advances,2012,2(10):4498-4506.
[17] Zhu S H,Cen Y L,Yang M,et al. Probing the intrinsic active sites of modified graphene oxide for aerobic benzylic alcohol oxidation[J]. Applied Catalysis B:Environmental,2017,211:89-97.
[18] Fierro V,Torné-Fernández V,Celzard A,et al. Influence of the demineralisation on the chemical activation of Kraft lignin with orthophosphoric acid[J]. Journal of Hazardous Materials,2007,149(1):126-133.
[19] Brindha A,Sivakumar T. Visible active N,S co-doped Ti O2/graphene photocatalysts for the degradation of hazardous dyes[J]. Journal of Photochemistry and Photobiology A:Chemistry,2017,340:146-156.
[20]王莹,魏成耀,黄天寅,等.氮掺杂碳纳米管活化过一硫酸盐降解酸性橙AO7[J].中国环境科学,2017,37(7):2583-2590.Wang Y, Wei C Y, Huang T Y, et al. Activation of peroxymonosulfate by nitrogen-doped carbon nanotubes to decolorize acid orange 7[J]. China Environmental Science,2017,37(7):2583-2590.
[21] Wu J C S,Lin H M,Lai C L. Photo reduction of CO2to methanol using optical-fiber photoreactor[J]. Applied Catalysis A:General,2005,296(2):194-200.
[22] Zhang T T,Li C,Gu Y,et al. Fabrication of novel metal-free"graphene alloy"for the highly efficient electrocatalytic reduction of H2O2[J]. Talanta,2017,165:143-151.
[23] Sheng Z H,Shao L,Chen J J,et al. Catalyst-free synthesis of nitrogen-doped graphene via thermal annealing graphite oxide with melamine and its excellent electrocatalysis[J]. ACS Nano,2011,5(6):4350-4358.
[24] Wohlgemuth S A,White R J,Willinger M G,et al. A one-pot hydrothermal synthesis of sulfur and nitrogen doped carbon aerogels with enhanced electrocatalytic activity in the oxygen reduction reaction[J]. Green Chemistry,2012,14(5):1515-1523.
[25] Xiong B,Zhou Y K,O'Hayre R,et al. Facile single-step ammonia heat-treatment and quenching process for the synthesis of improved Pt/N-graphene catalysts[J]. Applied Surface Science,2013,266:433-439.
[26] Liang P,Zhang C,Duan X G,et al. An insight into metal organic framework derived N-doped graphene for the oxidative degradation of persistent contaminants:formation mechanism and generation of singlet oxygen from peroxymonosulfate[J].Environmental Science:Nano,2017,4(2):315-324.
[27] Biddinger E J,von Deak D,Ozkan U S. Nitrogen-containing carbon nanostructures as oxygen-reduction catalysts[J]. Topics in Catalysis,2009,52(11):1566-1574.
[28] Lin Z Y,Waller G H,Liu Y,et al. Simple preparation of nanoporous few-layer nitrogen-doped graphene for use as an efficient electrocatalyst for oxygen reduction and oxygen evolution reactions[J]. Carbon,2013,53:130-136.
[29] Kudin K N,Ozbas B,Schniepp H C,et al. Raman spectra of graphite oxide and functionalized graphene sheets[J]. Nano Letters,2008,8(1):36-41.
[30] Sui N,Duan Y Z,Jiao X L,et al. Large-Scale preparation and catalytic properties of one-dimensionalα/β-MnO2nanostructures[J]. The Journal of Physical Chemistry C,2009,113(20):8560-8565.
[31] Xu L,Xu C,Zhao M R,et al. Oxidative removal of aqueous steroid estrogens by manganese oxides[J]. Water Research,2008,42(20):5038-5044.
[32] Deng J,Feng S F,Ma X Y,et al. Heterogeneous degradation of OrangeⅡwith peroxymonosulfate activated by ordered mesoporous MnFe2O4[J]. Separation and Purification Technology,2016,167:181-189.
[33]田凯勋,杨超,肖泉,等.超声强化零价铁/过硫酸钾体系降解2,4,6-三氯苯酚废水[J].中国环境科学,2017,37(10):3729-3734.Tian K X,Yang C,Xiao Q,et al. Degradation of 2,4,6-TCP in an ultrasound-enhanced zero-valent iron/potassium persulfate system[J]. China Environmental Science,2017,37(10):3729-3734.
[34] Zhao Z W,Zhao J H,Yang C. Efficient removal of ciprofloxacin by peroxymonosulfate/Mn3O4-MnO2catalytic oxidation system[J]. Chemical Engineering Journal,2017,327:481-489.
[35] Anipsitakis G P, Dionysiou D D. Degradation of organic contaminants in water with sulfate radicals generated by the conjunction of peroxymonosulfate with cobalt[J]. Environmental Science&Technology,2003,37(20):4790-4797.
[36] Yang S Y,Yang X,Shao X T,et al. Activated carbon catalyzed persulfate oxidation of Azo dye acid orange 7 at ambient temperature[J]. Journal of Hazardous Materials,2011,186(1):659-666.
[37] Liang H Y,Zhang Y Q,Huang S B,et al. Oxidative degradation of p-chloroaniline by copper oxidate activated persulfate[J].Chemical Engineering Journal,2013,218:384-391.
[2] Khan N E,Adewuyi Y G. Absorption and oxidation of nitric oxide(NO)by aqueous solutions of sodium persulfate in a bubble column reactor[J]. Industrial&Engineering Chemistry Research,2010,49(18):8749-8760.
[3]刘琰,孙德智.高级氧化技术处理染料废水的研究进展[J].工业水处理,2006,26(6):1-5.Liu Y,Sun D Z. Study progress of dye wastewater treatment by advanced oxidation processes[J]. Industrial Water Treatment,2006,26(6):1-5.
[4] Zhou G L,Sun H Q,Wang S B,et al. Titanate supported cobalt catalysts for photochemical oxidation of phenol under visible light irradiations[J]. Separation and Purification Technology,2011,80(3):626-634.
[5] Tan C Q,Gao N Y,Deng Y,et al. Heat-activated persulfate oxidation of diuron in water[J]. Chemical Engineering Journal,2012,203:294-300.
[6] Tan C Q,Gao N Y,Yang D,et al. Degradation of antipyrine by heat activated persulfate[J]. Separation and Purification Technology,2013,109:122-128.
[7] Shukla P,Sun H Q,Wang S B,et al. Nanosized Co3O4/SiO2for heterogeneous oxidation of phenolic contaminants in waste water[J]. Separation and Purification Technology,2011,77(2):230-236.
[8] Liang H W,Sun H Q,Patel A,et al. Excellent performance of mesoporous Co3O4/MnO2nanoparticles in heterogeneous activation of peroxymonosulfate for phenol degradation in aqueous solutions[J]. Applied Catalysis B:Environmental,2012,127:330-335.
[9] Kuila T,Bose S,Mishra A K,et al. Chemical functionalization of graphene and its applications[J]. Progress in Materials Science,2012,57(7):1061-1105.
[10] Zhang L P,Xia Z H. Mechanisms of oxygen reduction reaction on nitrogen-doped graphene for fuel cells[J]. The Journal of Physical Chemistry C,2011,115(22):11170-11176.
[11] Yao Y J,Xu C,Yu S M,et al. Facile synthesis of Mn3O4-reduced graphene oxide hybrids for catalytic decomposition of aqueous organics[J]. Industrial&Engineering Chemistry Research,2013,52(10):3637-3645.
[12]周雪君,时鹏辉,姚伟峰.掺氮石墨烯的制备及其催化性能研究[J].上海电力学院学报,2016,32(4):333-338.Zhou X J,Shi P H,Yao W F. Preparation and research of nitrogen-modified graphene[J]. Journal of Shanghai University of Electric Power,2016,32(4):333-338.
[13] Perera S D,Mariano R G,Vu K,et al. Hydrothermal synthesis of graphene-TiO2nanotube composites with enhanced photocatalytic activity[J]. ACS Catalysis,2012,2(6):949-956.
[14]吴丽颖,王炳煌,张圆春,等.凝胶球负载零价铁活化过硫酸盐降解偶氮染料废水[J].化工进展,2017,36(6):2318-2324.Wu L Y,Wang B H,Zhang Y C,et al. Degradation of reactive black5(RBk5)by gelatin balls loading iron activating sodium persulfate[J]. Chemical Industry and Engineering Progress,2017,36(6):2318-2324.
[15] Duan X G,O'donnell K,Sun H Q,et al. Sulfur and nitrogen Co-doped graphene for metal-free catalytic oxidation reactions[J]. Small,2015,11(25):3036-3044.
[16] Sun L,Wang L,Tian C G,et al. Nitrogen-doped graphene with high nitrogen level via a one-step hydrothermal reaction of graphene oxide with urea for superior capacitive energy storage[J]. RSC Advances,2012,2(10):4498-4506.
[17] Zhu S H,Cen Y L,Yang M,et al. Probing the intrinsic active sites of modified graphene oxide for aerobic benzylic alcohol oxidation[J]. Applied Catalysis B:Environmental,2017,211:89-97.
[18] Fierro V,Torné-Fernández V,Celzard A,et al. Influence of the demineralisation on the chemical activation of Kraft lignin with orthophosphoric acid[J]. Journal of Hazardous Materials,2007,149(1):126-133.
[19] Brindha A,Sivakumar T. Visible active N,S co-doped Ti O2/graphene photocatalysts for the degradation of hazardous dyes[J]. Journal of Photochemistry and Photobiology A:Chemistry,2017,340:146-156.
[20]王莹,魏成耀,黄天寅,等.氮掺杂碳纳米管活化过一硫酸盐降解酸性橙AO7[J].中国环境科学,2017,37(7):2583-2590.Wang Y, Wei C Y, Huang T Y, et al. Activation of peroxymonosulfate by nitrogen-doped carbon nanotubes to decolorize acid orange 7[J]. China Environmental Science,2017,37(7):2583-2590.
[21] Wu J C S,Lin H M,Lai C L. Photo reduction of CO2to methanol using optical-fiber photoreactor[J]. Applied Catalysis A:General,2005,296(2):194-200.
[22] Zhang T T,Li C,Gu Y,et al. Fabrication of novel metal-free"graphene alloy"for the highly efficient electrocatalytic reduction of H2O2[J]. Talanta,2017,165:143-151.
[23] Sheng Z H,Shao L,Chen J J,et al. Catalyst-free synthesis of nitrogen-doped graphene via thermal annealing graphite oxide with melamine and its excellent electrocatalysis[J]. ACS Nano,2011,5(6):4350-4358.
[24] Wohlgemuth S A,White R J,Willinger M G,et al. A one-pot hydrothermal synthesis of sulfur and nitrogen doped carbon aerogels with enhanced electrocatalytic activity in the oxygen reduction reaction[J]. Green Chemistry,2012,14(5):1515-1523.
[25] Xiong B,Zhou Y K,O'Hayre R,et al. Facile single-step ammonia heat-treatment and quenching process for the synthesis of improved Pt/N-graphene catalysts[J]. Applied Surface Science,2013,266:433-439.
[26] Liang P,Zhang C,Duan X G,et al. An insight into metal organic framework derived N-doped graphene for the oxidative degradation of persistent contaminants:formation mechanism and generation of singlet oxygen from peroxymonosulfate[J].Environmental Science:Nano,2017,4(2):315-324.
[27] Biddinger E J,von Deak D,Ozkan U S. Nitrogen-containing carbon nanostructures as oxygen-reduction catalysts[J]. Topics in Catalysis,2009,52(11):1566-1574.
[28] Lin Z Y,Waller G H,Liu Y,et al. Simple preparation of nanoporous few-layer nitrogen-doped graphene for use as an efficient electrocatalyst for oxygen reduction and oxygen evolution reactions[J]. Carbon,2013,53:130-136.
[29] Kudin K N,Ozbas B,Schniepp H C,et al. Raman spectra of graphite oxide and functionalized graphene sheets[J]. Nano Letters,2008,8(1):36-41.
[30] Sui N,Duan Y Z,Jiao X L,et al. Large-Scale preparation and catalytic properties of one-dimensionalα/β-MnO2nanostructures[J]. The Journal of Physical Chemistry C,2009,113(20):8560-8565.
[31] Xu L,Xu C,Zhao M R,et al. Oxidative removal of aqueous steroid estrogens by manganese oxides[J]. Water Research,2008,42(20):5038-5044.
[32] Deng J,Feng S F,Ma X Y,et al. Heterogeneous degradation of OrangeⅡwith peroxymonosulfate activated by ordered mesoporous MnFe2O4[J]. Separation and Purification Technology,2016,167:181-189.
[33]田凯勋,杨超,肖泉,等.超声强化零价铁/过硫酸钾体系降解2,4,6-三氯苯酚废水[J].中国环境科学,2017,37(10):3729-3734.Tian K X,Yang C,Xiao Q,et al. Degradation of 2,4,6-TCP in an ultrasound-enhanced zero-valent iron/potassium persulfate system[J]. China Environmental Science,2017,37(10):3729-3734.
[34] Zhao Z W,Zhao J H,Yang C. Efficient removal of ciprofloxacin by peroxymonosulfate/Mn3O4-MnO2catalytic oxidation system[J]. Chemical Engineering Journal,2017,327:481-489.
[35] Anipsitakis G P, Dionysiou D D. Degradation of organic contaminants in water with sulfate radicals generated by the conjunction of peroxymonosulfate with cobalt[J]. Environmental Science&Technology,2003,37(20):4790-4797.
[36] Yang S Y,Yang X,Shao X T,et al. Activated carbon catalyzed persulfate oxidation of Azo dye acid orange 7 at ambient temperature[J]. Journal of Hazardous Materials,2011,186(1):659-666.
[37] Liang H Y,Zhang Y Q,Huang S B,et al. Oxidative degradation of p-chloroaniline by copper oxidate activated persulfate[J].Chemical Engineering Journal,2013,218:384-391.