Preparation of porous semi-IPN temperature-sensitive hydrogel-supported nZVI and its application in the reduction of nitrophenol
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摘要
Nanoscale zero-valent iron(n ZVI) particles supported on a porous, semi-interpenetrating(semi-IPN), temperature-sensitive composite hydrogel(PNIPAm-PHEMA). n ZVI@PNIPAmPHEMA, was successfully synthesized and characterized by FT-IR, SEM, EDS, XRD and the weighing method. The loading of nZVI was 0.1548 ± 0.0015 g/g and the particle size was30–100 nm. NZVI was uniformly dispersed on the pore walls inside the PNIPAm-PHEMA.Because of the well-dispersed n ZVI, the highly porous structure, and the synergistic effect of PNIPAm-PHEMA, nZVI@PNIPAm-PHEMA showed excellent reductive activity and wide p H applicability. 95% of 4-NP in 100 m L of 400 mg/L 4-NP solution with initial p H 3.0–9.0 could be completely reduced into 4-AP by about 0.0548 g of fresh supported n ZVI at 18–25 °C under stirring(110 r/min) within 45 min reaction time. A greater than 99% 4-NP degradation ratio was obtained when the initial p H was 5.0–9.0. The reduction of 4-NP by nZVI@PNIPAm-PHEMA was in agreement with the pseudo-first-order kinetics model with Kobsvalues of 0.0885–0.101 min-1.NZVI@PNIPAm-PHEMA was able to be recycled, and about 85% degradation ratio of 4-NP was obtained after its sixth reuse cycle. According to the temperature sensitivity of PNIPAmPHEMA, n ZVI@PNIPAm-PHEMA exhibited very good storage stability, and about 88.9%degradation ratio of 4-NP was obtained after its storage for 30 days. The hybrid reducer was highly efficient for the reduction of 2-NP, 3-NP, 2-chloro-4-nitrophenol and 2-chloro-4-nitrophenol. Our results suggest that PNIPAm-PHEMA could be a good potential carrier, with n ZVI@PNIPAm-PHEMA having potential value in the application of reductive degradation of nitrophenol pollutants.
Nanoscale zero-valent iron(n ZVI) particles supported on a porous, semi-interpenetrating(semi-IPN), temperature-sensitive composite hydrogel(PNIPAm-PHEMA). n ZVI@PNIPAmPHEMA, was successfully synthesized and characterized by FT-IR, SEM, EDS, XRD and the weighing method. The loading of nZVI was 0.1548 ± 0.0015 g/g and the particle size was30–100 nm. NZVI was uniformly dispersed on the pore walls inside the PNIPAm-PHEMA.Because of the well-dispersed n ZVI, the highly porous structure, and the synergistic effect of PNIPAm-PHEMA, nZVI@PNIPAm-PHEMA showed excellent reductive activity and wide p H applicability. 95% of 4-NP in 100 m L of 400 mg/L 4-NP solution with initial p H 3.0–9.0 could be completely reduced into 4-AP by about 0.0548 g of fresh supported n ZVI at 18–25 °C under stirring(110 r/min) within 45 min reaction time. A greater than 99% 4-NP degradation ratio was obtained when the initial p H was 5.0–9.0. The reduction of 4-NP by nZVI@PNIPAm-PHEMA was in agreement with the pseudo-first-order kinetics model with Kobsvalues of 0.0885–0.101 min-1.NZVI@PNIPAm-PHEMA was able to be recycled, and about 85% degradation ratio of 4-NP was obtained after its sixth reuse cycle. According to the temperature sensitivity of PNIPAmPHEMA, n ZVI@PNIPAm-PHEMA exhibited very good storage stability, and about 88.9%degradation ratio of 4-NP was obtained after its storage for 30 days. The hybrid reducer was highly efficient for the reduction of 2-NP, 3-NP, 2-chloro-4-nitrophenol and 2-chloro-4-nitrophenol. Our results suggest that PNIPAm-PHEMA could be a good potential carrier, with n ZVI@PNIPAm-PHEMA having potential value in the application of reductive degradation of nitrophenol pollutants.
Nanoscale zero-valent iron(n ZVI) particles supported on a porous, semi-interpenetrating(semi-IPN), temperature-sensitive composite hydrogel(PNIPAm-PHEMA). n ZVI@PNIPAmPHEMA, was successfully synthesized and characterized by FT-IR, SEM, EDS, XRD and the weighing method. The loading of nZVI was 0.1548 ± 0.0015 g/g and the particle size was30–100 nm. NZVI was uniformly dispersed on the pore walls inside the PNIPAm-PHEMA.Because of the well-dispersed n ZVI, the highly porous structure, and the synergistic effect of PNIPAm-PHEMA, nZVI@PNIPAm-PHEMA showed excellent reductive activity and wide p H applicability. 95% of 4-NP in 100 m L of 400 mg/L 4-NP solution with initial p H 3.0–9.0 could be completely reduced into 4-AP by about 0.0548 g of fresh supported n ZVI at 18–25 °C under stirring(110 r/min) within 45 min reaction time. A greater than 99% 4-NP degradation ratio was obtained when the initial p H was 5.0–9.0. The reduction of 4-NP by nZVI@PNIPAm-PHEMA was in agreement with the pseudo-first-order kinetics model with Kobsvalues of 0.0885–0.101 min-1.NZVI@PNIPAm-PHEMA was able to be recycled, and about 85% degradation ratio of 4-NP was obtained after its sixth reuse cycle. According to the temperature sensitivity of PNIPAmPHEMA, n ZVI@PNIPAm-PHEMA exhibited very good storage stability, and about 88.9%degradation ratio of 4-NP was obtained after its storage for 30 days. The hybrid reducer was highly efficient for the reduction of 2-NP, 3-NP, 2-chloro-4-nitrophenol and 2-chloro-4-nitrophenol. Our results suggest that PNIPAm-PHEMA could be a good potential carrier, with n ZVI@PNIPAm-PHEMA having potential value in the application of reductive degradation of nitrophenol pollutants.
引文
Agnieszka,H.D.,Jolanta,B.,Andrzej,W.T.,2007.Immobilization of glucoamylase and trypsin on crosslinked thermosensitive carriers.Enzyme Microb.Tech.41,197-204.
Bard,A.J.,Faulkner,L.R.,2001.Electrochemical Methods:Fundamentals and Applications.2nd edition.Wiley,New York.
Buwalda,S.J.,Boere,K.W.M.,Dijkstra,P.J.,Feijen,J.,Vermonden,T.,Hennink,W.E.,2014.Hydrogels in a historical perspective:from simple networks to smart materials.J.Control.Release190,254-273.
Comba,S.,Di Molfetta,A.,Sethi,R.,2011.A comparison between field applications of nano-,micro-,and millimetric zero-valent iron for the remediation of contaminated aquifers.Water Air Soil Poll.215,595-607.
Cook,M.T.,Filippov,S.K.,Khutoryanskiy,V.V.,2017.Synthesis and solution properties of a temperature-responsive PNIPAM-bPDMS-b-PNIPAM triblock copolymer.Colloid Polym.Sci.295,1351-1358.
Ezzatahmadi,N.,Ayoko,G.A.,Millar,G.J.,Speight,R.,Yan,C.,Li,J.H.,et al.,2017.Clay-supported nanoscale zero-valent iron composite materials for the remediation of contaminated aqueous solutions:a review.Chem.Eng.J.312,336-350.
Fang,Z.,Chen,J.,Qiu,X.,Cheng,W.,Zhu,L.,2011.Effective removal of antibiotic metronidazole from water by nanoscale zero-valent iron particles.Desalination 268,60-67.
Gao,Y.Z.,He,Y.,Zhao,Y.P.,Chen,L.,Yan,F.Y.,2016.Fabrication of thermoseneitive hydrogel-supported Ni nanoparticles with tunable catalytic activity for 4-nitrophenol.J.Mater.Sci.51,3200-3210.
Gillham,R.W.,O'Hannesin,S.F.,1994.Enhanced degradation of halogenated aliphatics by zero-valent iron.Ground Water 32,958-967.
Heskins,M.,Guillet,J.E.,1968.Solution properties of poly(N-isopropylacrylamide).J.Macromol.Sci.Chem.1441-1455 A2.
Horzum,N.,Demir,M.M.,Nairat,M.,Shahwan,T.,2013.Chitosan fiber-supported zero-valent iron nanoparticles as a novel sorbent for sequestration of inorganic arsenic.RSC Adv.3,7828-7837.
Jiang,Z.M.,Lv,L.,Zhang,W.M.,Du,Q.,Pan,B.C.,Yang,L.,et al.,2011.Nitrate reduction using nanosized zero-valent iron supported by polystyrene resins:role of surface functional groups.Water Res.45,2191-2198.
Kawaguchi,H.,2014.Thermoresponsive microhydrogels:preparation,properties and applications.Polym.Int.63,925-932.
Klaikherd,A.,Nagamani,C.,Thayumanavan,S.,2009.Multistimuli sensitive amphiphilic block copolymer assemblies.J.Am.Chem.Soc.131,4830-4838.
Lai,B.,Zhang,Y.H.,Li,R.,Zhou,Y.X.,Wang,J.l.,2014.Influence of operating of operating temperature on the reduction of high concentration p-nitrophenol(PNP)by zero valent iron(ZVI).Chem.Eng.J.249,143-152.
Li,L.X.,Xing,X.D.,Liu,Z.L.,2012.Triply-responsive(thermo/light/p H)copolymeric hydrogel of N-Isopropylacrylamide with an azobenzene-containing monomer.J.Appl.Polym.Sci.124,1128-1136.
Li,L.X.,Lu,B.,Zhang,Y.,Xing,X.D.,Wu,X.Y.,Liu,Z.L.,2015.Multisensitive copolymer hydrogels of N-isopropylacrylamide with several polymerizable azobenzene-containing monomers.J.Polym.Res.22,176-188.
Li,L.X.,Zhang,S.S.,Lu,B.,Zhu,F.,Cheng,J.,Sun,Z.H.,2018.Nitrobenzene reduction using nanoscale zero-valent iron supported by polystyrene microspheres with different surface functional groups.Environ.Sci.Pollut.Res.25(8),7916-7923.
Liang,C.J.,Lin,Y.T.,Shiu,J.W.,2015.Reduction of nitrobenzene with alkaline ascorbic acid:kinetics and pathways.J.Hazard.Mater.302,137-143.
Liu,H.B.,Chen,T.H.,Xie,Q.Q.,Zou,X.H.,Chen,C.,Frost,R.L.,2015.The functionalization of limonite to prepare NZVI and its application in decomposition of p-nitrophenol.J.Nanopart.Res.17,374-381.
Lofrano,G.,Libralato,G.,Brown,J.,2017.Nanotechnologies for Environmental Remediation:Applications and Implications,Nanomaterials for Adsorption and Heterogeneous Reaction in Water Decontamination.Springer International Publishing AG,pp.200-201.
Natassa,P.,Anastasia,M.,Stergios,P.,Costas,D.,2017.Lysozyme complexes with thermo-and pH-responsive PNIPAM-b-PAAblock copolymer.J.Nanopart.Res.1976-1982.
Noubactep,C.,2010.The fundamental mechanism of aqueous contaminant removal by metallic iron.Water SA 36,663-670.
Noubactep,C.,Caré,S.,Crane,R.,2012.Nanoscale metallic Iron for environmental remediation:prospects and limitations.Water Air Soil Poll.223,1363-1382.
Parshetti,G.K.,Doong,R.A.,2009.Dechlorination of trichloroethylene by Ni/Fe nanoparticles immobilized in PEG/PVDF and PEG/nylon 66 membranes.Water Res.43,3086-3094.
Schild,H.G.,1992.Poly(N-isopropylacrylamide):experiment,theory and application.Prog.Polym.Sci.17,163-249.
Sohn,K.,Kang,S.W.,Ahn,S.,Woo,M.,Yang,S.K.,2006.Fe(0)nanoparticles for nitrate reduction:stability,reactivity,and transformation.Environ.Sci.Technol.40,5514-5519.
Stefaniuk,M.,Oleszczuk,P.,Ok,Y.S.,2016.Review on nano zerovalent iron(nZVI):from synthesis to environmental applications.Chem.Eng.J.287,618-632.
Sulu,E.,Biswas,C.S.,Stadler,F.J.,Hazer,B.,2017.Synthesis,characterization,and drug release properties of macroporous dual stimuli responsive stereo regular nanocomposites gels of poly(N-isopropylacrylamide)and graphene oxide.J.Porous Mat.24,389-401.
Tang,L.,Tang,J.,Zeng,G.M.,Yang,G.D.,Xie,X.,Zhou,Y.Y.,et al.,2015.Rapid reductive degradation of aqueous p-nitropehnol using nanoscale zero-valent iron particles immobilized on mesoporous silica with enhanced antioxidation effect.Appl.Surf.Sci.333,220-228.
Tauer,K.,Gau,D.,Schulze,S.,V?lkel,A.,Dimova,R.,2009.Thermal property changes of poly(N-isopropylacrylamide)microgel particles and block copolymers.Colloid Polym.Sci.287,299-312.
Wang,C.B.,Zhang,W.,1997.Synthesizing nanoscale iron particles for rapid and complete dechlorination of TCE and PCBs.Environ.Sci.Technol.31,2154-2156.
Wang,Y.,Zhang,J.Z.,Zhang,W.Q.,Zhang,M.C.,2009.Pdcatalyzed C-C cross-coupling reactions within a thermoresponsive and p H-responsive and chelating polymeric hydrogel.J.Org.Chem.74,1923-1931.
Yan,J.,Han,L.,Gao,W.,Xue,S.,Chen,M.,2015.Biochar supported nanoscale zerovalent iron composite used as persulfate activator for removing trichloroethylene.Bioresour.Technol.175,269-274.
Yi,G.B.,Huang,Y.W.,Xiong,F.H.,Liao,B.,Yang,J.,Chen,X.D.,2011.Preparation and swelling behaviors of rapid responsive semi-IPN NaCMC/PNIPAm hydrogels.J.Wuhan Univ.Technol.Mater.Sci.Ed.26,1073-1078.
Zhang,G.Q.,Zha,L.S.,Zhou,M.H.,Liang,B.R.,2005.Rapid deswelling of sodium alginate/poly(N-isopropylacrylamide)semi-interpenetrating polymer network hydrogels in response to temperature and p H changes.Colloid Polym.Sci.283,431-438.
Zhang,Q.R.,Du,Q.,Hua,M.,Jiao,T.F.,Gao,F.M.,Pan,B.C.,2013.Sorption enhancement of Lead ions from water by surface charged polystyrene-supported Nano-zirconium oxide composites.Environ.Sci.Technol.47,6536-6544.
Zhang,W.,Yu,T.,Han,X.L.,Ying,W.C.,2016.Removal of 2-ClBPfrom soil-water system using activated carbon supported nanoscale zerovalent iron.J.Environ.Sci.47,143-152.
Zhao,X.,Lv,L.,Pan,B.C.,Zhang,W.M.,Zhang,S.J.,Zhang,Q.X.,2011.Polymer-supported nanocomposites for environmental application:a review.Chem.Eng.J.170,381-394.
Bard,A.J.,Faulkner,L.R.,2001.Electrochemical Methods:Fundamentals and Applications.2nd edition.Wiley,New York.
Buwalda,S.J.,Boere,K.W.M.,Dijkstra,P.J.,Feijen,J.,Vermonden,T.,Hennink,W.E.,2014.Hydrogels in a historical perspective:from simple networks to smart materials.J.Control.Release190,254-273.
Comba,S.,Di Molfetta,A.,Sethi,R.,2011.A comparison between field applications of nano-,micro-,and millimetric zero-valent iron for the remediation of contaminated aquifers.Water Air Soil Poll.215,595-607.
Cook,M.T.,Filippov,S.K.,Khutoryanskiy,V.V.,2017.Synthesis and solution properties of a temperature-responsive PNIPAM-bPDMS-b-PNIPAM triblock copolymer.Colloid Polym.Sci.295,1351-1358.
Ezzatahmadi,N.,Ayoko,G.A.,Millar,G.J.,Speight,R.,Yan,C.,Li,J.H.,et al.,2017.Clay-supported nanoscale zero-valent iron composite materials for the remediation of contaminated aqueous solutions:a review.Chem.Eng.J.312,336-350.
Fang,Z.,Chen,J.,Qiu,X.,Cheng,W.,Zhu,L.,2011.Effective removal of antibiotic metronidazole from water by nanoscale zero-valent iron particles.Desalination 268,60-67.
Gao,Y.Z.,He,Y.,Zhao,Y.P.,Chen,L.,Yan,F.Y.,2016.Fabrication of thermoseneitive hydrogel-supported Ni nanoparticles with tunable catalytic activity for 4-nitrophenol.J.Mater.Sci.51,3200-3210.
Gillham,R.W.,O'Hannesin,S.F.,1994.Enhanced degradation of halogenated aliphatics by zero-valent iron.Ground Water 32,958-967.
Heskins,M.,Guillet,J.E.,1968.Solution properties of poly(N-isopropylacrylamide).J.Macromol.Sci.Chem.1441-1455 A2.
Horzum,N.,Demir,M.M.,Nairat,M.,Shahwan,T.,2013.Chitosan fiber-supported zero-valent iron nanoparticles as a novel sorbent for sequestration of inorganic arsenic.RSC Adv.3,7828-7837.
Jiang,Z.M.,Lv,L.,Zhang,W.M.,Du,Q.,Pan,B.C.,Yang,L.,et al.,2011.Nitrate reduction using nanosized zero-valent iron supported by polystyrene resins:role of surface functional groups.Water Res.45,2191-2198.
Kawaguchi,H.,2014.Thermoresponsive microhydrogels:preparation,properties and applications.Polym.Int.63,925-932.
Klaikherd,A.,Nagamani,C.,Thayumanavan,S.,2009.Multistimuli sensitive amphiphilic block copolymer assemblies.J.Am.Chem.Soc.131,4830-4838.
Lai,B.,Zhang,Y.H.,Li,R.,Zhou,Y.X.,Wang,J.l.,2014.Influence of operating of operating temperature on the reduction of high concentration p-nitrophenol(PNP)by zero valent iron(ZVI).Chem.Eng.J.249,143-152.
Li,L.X.,Xing,X.D.,Liu,Z.L.,2012.Triply-responsive(thermo/light/p H)copolymeric hydrogel of N-Isopropylacrylamide with an azobenzene-containing monomer.J.Appl.Polym.Sci.124,1128-1136.
Li,L.X.,Lu,B.,Zhang,Y.,Xing,X.D.,Wu,X.Y.,Liu,Z.L.,2015.Multisensitive copolymer hydrogels of N-isopropylacrylamide with several polymerizable azobenzene-containing monomers.J.Polym.Res.22,176-188.
Li,L.X.,Zhang,S.S.,Lu,B.,Zhu,F.,Cheng,J.,Sun,Z.H.,2018.Nitrobenzene reduction using nanoscale zero-valent iron supported by polystyrene microspheres with different surface functional groups.Environ.Sci.Pollut.Res.25(8),7916-7923.
Liang,C.J.,Lin,Y.T.,Shiu,J.W.,2015.Reduction of nitrobenzene with alkaline ascorbic acid:kinetics and pathways.J.Hazard.Mater.302,137-143.
Liu,H.B.,Chen,T.H.,Xie,Q.Q.,Zou,X.H.,Chen,C.,Frost,R.L.,2015.The functionalization of limonite to prepare NZVI and its application in decomposition of p-nitrophenol.J.Nanopart.Res.17,374-381.
Lofrano,G.,Libralato,G.,Brown,J.,2017.Nanotechnologies for Environmental Remediation:Applications and Implications,Nanomaterials for Adsorption and Heterogeneous Reaction in Water Decontamination.Springer International Publishing AG,pp.200-201.
Natassa,P.,Anastasia,M.,Stergios,P.,Costas,D.,2017.Lysozyme complexes with thermo-and pH-responsive PNIPAM-b-PAAblock copolymer.J.Nanopart.Res.1976-1982.
Noubactep,C.,2010.The fundamental mechanism of aqueous contaminant removal by metallic iron.Water SA 36,663-670.
Noubactep,C.,Caré,S.,Crane,R.,2012.Nanoscale metallic Iron for environmental remediation:prospects and limitations.Water Air Soil Poll.223,1363-1382.
Parshetti,G.K.,Doong,R.A.,2009.Dechlorination of trichloroethylene by Ni/Fe nanoparticles immobilized in PEG/PVDF and PEG/nylon 66 membranes.Water Res.43,3086-3094.
Schild,H.G.,1992.Poly(N-isopropylacrylamide):experiment,theory and application.Prog.Polym.Sci.17,163-249.
Sohn,K.,Kang,S.W.,Ahn,S.,Woo,M.,Yang,S.K.,2006.Fe(0)nanoparticles for nitrate reduction:stability,reactivity,and transformation.Environ.Sci.Technol.40,5514-5519.
Stefaniuk,M.,Oleszczuk,P.,Ok,Y.S.,2016.Review on nano zerovalent iron(nZVI):from synthesis to environmental applications.Chem.Eng.J.287,618-632.
Sulu,E.,Biswas,C.S.,Stadler,F.J.,Hazer,B.,2017.Synthesis,characterization,and drug release properties of macroporous dual stimuli responsive stereo regular nanocomposites gels of poly(N-isopropylacrylamide)and graphene oxide.J.Porous Mat.24,389-401.
Tang,L.,Tang,J.,Zeng,G.M.,Yang,G.D.,Xie,X.,Zhou,Y.Y.,et al.,2015.Rapid reductive degradation of aqueous p-nitropehnol using nanoscale zero-valent iron particles immobilized on mesoporous silica with enhanced antioxidation effect.Appl.Surf.Sci.333,220-228.
Tauer,K.,Gau,D.,Schulze,S.,V?lkel,A.,Dimova,R.,2009.Thermal property changes of poly(N-isopropylacrylamide)microgel particles and block copolymers.Colloid Polym.Sci.287,299-312.
Wang,C.B.,Zhang,W.,1997.Synthesizing nanoscale iron particles for rapid and complete dechlorination of TCE and PCBs.Environ.Sci.Technol.31,2154-2156.
Wang,Y.,Zhang,J.Z.,Zhang,W.Q.,Zhang,M.C.,2009.Pdcatalyzed C-C cross-coupling reactions within a thermoresponsive and p H-responsive and chelating polymeric hydrogel.J.Org.Chem.74,1923-1931.
Yan,J.,Han,L.,Gao,W.,Xue,S.,Chen,M.,2015.Biochar supported nanoscale zerovalent iron composite used as persulfate activator for removing trichloroethylene.Bioresour.Technol.175,269-274.
Yi,G.B.,Huang,Y.W.,Xiong,F.H.,Liao,B.,Yang,J.,Chen,X.D.,2011.Preparation and swelling behaviors of rapid responsive semi-IPN NaCMC/PNIPAm hydrogels.J.Wuhan Univ.Technol.Mater.Sci.Ed.26,1073-1078.
Zhang,G.Q.,Zha,L.S.,Zhou,M.H.,Liang,B.R.,2005.Rapid deswelling of sodium alginate/poly(N-isopropylacrylamide)semi-interpenetrating polymer network hydrogels in response to temperature and p H changes.Colloid Polym.Sci.283,431-438.
Zhang,Q.R.,Du,Q.,Hua,M.,Jiao,T.F.,Gao,F.M.,Pan,B.C.,2013.Sorption enhancement of Lead ions from water by surface charged polystyrene-supported Nano-zirconium oxide composites.Environ.Sci.Technol.47,6536-6544.
Zhang,W.,Yu,T.,Han,X.L.,Ying,W.C.,2016.Removal of 2-ClBPfrom soil-water system using activated carbon supported nanoscale zerovalent iron.J.Environ.Sci.47,143-152.
Zhao,X.,Lv,L.,Pan,B.C.,Zhang,W.M.,Zhang,S.J.,Zhang,Q.X.,2011.Polymer-supported nanocomposites for environmental application:a review.Chem.Eng.J.170,381-394.
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