Reduced graphene oxide supported Fe/Ni nanocomposites for 2,4-dichlorophenol removal
HUANG Xue-zheng1,2,3, ZHANG Yong-xiang2, ZHANG Da-sheng4, ZHU Xin-feng1, LI Hou-yun1
1. Henan Province Key Laboratory of Water Pollution Control and Rehabilitation Technology, Henan University of Urban Construction, Pingdingshan 467000, China; 2. Department of Urban Construction, Beijing University of Technology, Beijing 100124, China; 3. School of Civil Engineering, Nanyang Institute of Technology, Nanyang 473000, China; 4. Hebei Institute of Water Science, Shijiazhuang 050051, China
Abstract：Reduced graphene oxide supported Fe/Ni nanocomposites were prepared for the rapid and effective adsorption and dechlorination of 2,4-dichlorophenol (2,4-DCP) by using liquid phase reduction method. The morphological characterization showed that the spherical Fe/Ni bimetallic nanoparticles with the size of 80~150nm were successfully inserted into the graphene sheets and mainly distributed at the edges and folds of the graphene sheets. The agglomeration of Fe/Ni nanoparticles decreased significantly. XRD patterns and FTIR analysis showed nZVI nanoparticles were successfully embedded into graphene through Fe-O bond, Fe/Ni bimetallic nanoparticles had poor crystallinity and amorphous iron oxide which covered the outer layer of nanoparticles. The effects of different preparation conditions such as carbon iron ratio, nickel loading and reduction degree of graphene oxide on the removal of 2,4-DCP were discussed. The optimum preparation conditions of the Fe/Ni@rGO composites are as follows: the mass ratio of graphene to Fe is 1:2, the Ni loading is 5%, and the molar ratio of NaBH4to Fe2+ is 5:1. The adsorption and dechlorination perfermance of 2,4-DCP by nZVI, Fe/Ni, Fe@rGO composites and Fe/Ni@rGO composites were compared and analyzed. The results showed that the removal efficiency of 2,4-DCP by five materials followed the sequence: Fe/Ni@rGOcomposites>Fe/Ni>rGO>Fe@rGOcomposites>nZVI. However, the cycle test and storage stability test showed: compared with Fe/Ni bimetallic, Fe/Ni@rGO composites had stable reactivity activity and high reruse value. The results demonstrated the removal mechanism of 2,4-DCP by Fe/Ni@rGO composites was the synergistic effect of adsorption and dechlorination.
[1] Garba Z N, Zhou W, Lawan I, et al. An overview of chlorophenols as contaminants and their removal from wastewater by adsorption: A review[J]. Journal of Environmental Management, 2019,241:59-75. [2] Wu C, Zhou L, Zhou C, et al. A kinetic model for 2,4-dichlorophenol adsorption and hydrodechlorination over a palladized biofilm[J]. Water Research, 2022,214:118201. [3] 朱菲菲,秦普丰,张娟,等.我国地下水环境优先控制有机污染物的筛选[J]. 环境工程技术学报, 2013,3(5):443-50. Zhu F F, Qin P F, Zhang J. et al. Screening of priority organic pollutants in groundwater of China[J]. Journal of Environmental Engineering Technology, 2013,3(5):443-50. [4] Shah J, Jan M R, Iqbal M, et al. Mixed hemimicelles silica-coated magnetic nanoparticles for solid-phase extraction of chlorophenols from different water samples[J]. Desalination and water treatment, 2018,112:310-318. [5] Pang H, Liu L, Bai Z, et al. Fabrication of sulfide nanoscale zero- valent iron and heterogeneous Fenton-like degradation of 2, 4-Dichlorophenol[J]. Separation and Purification Technology, 2022, 285:120408. [6] 郭汶俊,张永祥,井琦,等.CMS包覆纳米零价铁去除2,4-二氯酚的条件优化[J]. 环境工程学报, 2018,12(12):3289-3296. Guo W J, Zhang Y X, Jing Q, et al. Conditions optimization for 2, 4-dichlorophenol removal by CMS-coating nano zero-valent iron[J]. Chinese Journal of Environmental Engineering, 2018,12(12):3289-3296. [7] Eker S, Kargi F. Biological treatment of 2,4-dichlorophenol containing synthetic wastewater using a rotating brush biofilm reactor[J]. Bioresource Technology, 2008,99(7):2319-2325. [8] Wei D, Zhao C, Khan A, et al. Sorption mechanism and dynamic behavior of graphene oxide as an effective adsorbent for the removal of chlorophenol based environmental-hormones: A DFT and MD simulation study[J]. Chemical Engineering Journal, 2019,375:121964. [9] Ma J W, Wang H, Wang F Y, et al. Adsorption of 2,4-dichlorophenol from Aqueous Solution by a New Low-Cost Adsorbent-Activated Bamboo Charcoal[J]. Separation Science & Technology, 2010,45(16): 2329-2336. [10] Zhou P, Zhang J, Zhang Y L, et al. Degradation of 2,4-dichlorophenol by activating persulfate and peroxomonosulfate using micron or nanoscale zero-valent copper[J]. Journal of Hazardous Materials, 2018,344:1209-1219. [11] Gillham R W. Enhanced degradation of halogenated aliphatics by zero-valent iron[J]. Groundwater, 1994,32(6):958-967. [12] Wang C B, Zhang W X. Synthesizing nanoscale iron particles for rapid and complete dechlorination of TCE and PCBs[J]. Environmental Science & Technology, 1997,31(7):9602-9607. [13] Ahmad S, Liu X, Tang J, et al. Biochar-supported nanosized zero- valent iron (nZVI/BC) composites for removal of nitro and chlorinated contaminants[J]. Chemical Engineering Journal, 2022,431:133187. [14] Tan W, Ruan Y, Diao Z, et al. Removal of levofloxacin through adsorption and peroxymonosulfate activation using carbothermal reduction synthesized nZVI/carbon fiber[J]. Chemosphere, 2021,280: 130626. [15] Liang L, Li X, Guo Y, et al. The removal of heavy metal cations by sulfidated nanoscale zero-valent iron (S-nZVI): The reaction mechanisms and the role of sulfur[J]. Journal of Hazardous Materials, 2021,404:124057. [16] Gu M, Farooq U, Lu S, et al. Degradation of trichloroethylene in aqueous solution by rGO supported nZVI catalyst under several oxic environments[J]. Journal of Hazardous Materials, 2018,349:35-44. [17] Wu C, Liu W, Jing Z, et al. Mechanisms of synergistic removal of low concentration As(V) by nZVI@Mg(OH)2 nanocomposite[J]. The Journal of Physical Chemistry C, 2017,121(39):21411-21419. [18] Tang L, Yang G D, Zeng G M, et al. Synergistic effect of iron doped ordered mesoporous carbon on adsorption-coupled reduction of hexavalent chromium and the relative mechanism study[J]. Chemical Engineering Journal, 2014,239:114-122. [19] Xu J, Sheng T, Hu Y, et al. Adsorption-dechlorination of 2,4- dichlorophenol using two specified MWCNTs-stabilized Pd/Fe nanocomposites[J]. Chemical Engineering Journal, 2013,219:162-173. [20] 孙鸣璐,董军,张梦玥,等.乳化纳米铁(EZVI)强化地下水氯代烃还原脱氯[J]. 中国环境科学, 2022,42(6):2690-2696. Sun M L, Dong J, Zhang M Y, et al. Enhanced reductive dechlorination of chlorinated hydrocarbons in groundwater by emulsified zero-valentiron[J]. China Environmental Science, 2022, 42(6):2690-2696. [21] 朱颖一,王城晨,王明新,等.硫化纳米铁反应带修复硝基苯污染地下水[J]. 中国环境科学, 2020,40(2):670-680. Zhu Y Y, Wang C C, Wang M X, et al. Remediation of nitrobenzene contaminated groundwater by S-NZVI reaction zone[J]. China Environmental Science, 2020,40(2):670-680. [22] Cheng Y, Dong H, Hao T. CaCO3 coated nanoscale zero-valent iron (nZVI) for the removal of chromium (VI) in aqueous solution[J]. Separation and Purification Technology, 2021,257:117967. [23] Sun Y P, Li X Q, Cao J, et al. Characterization of zero-valent iron nanoparticles[J].Advances in Colloid and Interface Science, 2006, 120(1-3):47-56. [24] Chen H, Cao Y, Wei E, et al. Facile synthesis of graphene nano zero- valent iron composites and their efficient removal of trichloronitromethane from drinking water[J]. Chemosphere, 2016, 146:32-39. [25] Sahu R S, Bindumadhavan K, Doong R. Boron-doped reduced graphene oxide-based bimetallic Ni/Fe nanohybrids for the rapid dechlorination of trichloroethylene[J]. Environmental Science: Nano, 2017,4(3):565-576. [26] Sun Y P, Li X, Cao J, et al. Characterization of zero-valent iron nanoparticles[J]. Advances in Colloid and Interface Science, 2006,120(1-3):47-56. [27] Huang K, Bian H, Zhang M, et al. Characterization of bimetallic Fe/Ni nanoparticles supported by amphiphilic block copolymer and its application in removal of 1,1,1-trichloroethane in water[J]. Environmental Science and Pollution Research, 2020,27(27):34503-34512. [28] Masud A, Soria N G C, Aga D S, et al. Adsorption and advanced oxidation of diverse pharmaceuticals and personal care products (PPCPs) from water using highly efficient rGO-nZVI nanohybrids[J]. Environmental Science: Water Research & Technology, 2020,6(8): 2223-2238. [29] Xing R, He J, Hao P, et al. Graphene oxide-supported nanoscale zero-valent iron composites for the removal of atrazine from aqueous solution[J]. Colloids and Surfaces A: Physicochemical and Engineering Aspects, 2020,589:124466. [30] Gu M B, Farooq U, LU S G, et al. Degradation of trichloroethylene in aqueous solution by rGO supported nZVI catalyst under several oxic environments[J]. Journal of Hazardous Materials, 2018,349:35-44. [31] Ai Z, Gao Z, Zhang L, et al. Core-shell structure dependent reactivity of Fe@Fe2O3 nanowires on aerobic degradation of 4-chlorophenol[J]. Environ Sci Technol, 2013,47(10):5344-5352. [32] Sun Y, Ding C, Cheng W, et al. Simultaneous adsorption and reduction of U(VI) on reduced graphene oxide-supported nanoscale zerovalent iron[J]. Journal of Hazardous Materials, 2014,280:399-408. [33] Chandra V, Park J, Chun Y, et al. Water-dispersible magnetite-reduced graphene oxide composites for arsenic removal[J]. ACS Nano, 2010, 4(7):3979-3986. [34] Gu M, FAROOQ U, LU S, et al. Degradation of trichloroethylene in aqueous solution by rGO supported nZVI catalyst under several oxic environments[J]. Journal of Hazardous Materials, 2018,349(5):35-44. [35] Deosarkar M P, Pawar S M, Bhanvase B A. In situ sonochemical synthesis of Fe3O4-graphene nanocomposite for lithium rechargeable batteries[J]. Chemical Engineering and Processing: Process Intensification, 2014,83:49-55. [36] Wu S, He H, Li X, et al. Insights into atrazine degradation by persulfate activation using composite of nanoscale zero-valent iron and graphene: Performances and mechanisms[J]. Chemical Engineering Journal, 2018,341:126-136. [37] Zhang Q, Zhao D, Ding Y, et al. Synthesis of Fe-Ni/graphene oxide composite and its highly efficient removal of uranium(VI) from aqueous solution[J]. Journal of Cleaner Production, 2019,230:1305-1315. [38] He Y, Hai L, Dong Y, et al. Zeolite supported Fe/Ni bimetallic nanoparticles for simultaneous removal of nitrate and phosphate: Synergistic effect and mechanism[J]. Chemical Engineering Journal, 2018,347:669-681. [39] Xu J, Tan L, Baig S A, et al. Dechlorination of 2,4-dichlorophenol by nanoscale magnetic Pd/Fe particles: Effects of pH, temperature, common dissolved ions and humic acid[J]. Chemical Engineering Journal, 2013,231:26-35. [40] Zhang Z, Shen Q, Cissoko N, et al. Catalytic dechlorination of 2, 4-dichlorophenol by Pd/Fe bimetallic nanoparticles in the presence of humic acid[J]. Journal of Hazardous Materials, 2010,182(1-3):252-258. [41] Han J, Deming R L, Tao F M. Theoretical study of molecular structures and properties of the complete series of chlorophenols[J]. Journal of Physical Chemistry A, 2004,108(38):7736-7743. [42] Feng J, Lim T T. Pathways and kinetics of carbon tetrachloride and chloroform reductions by nano-scale Fe and Fe/Ni particles: comparison with commercial micro-scale Fe and Zn[J]. Chemosphere, 2005,59(9):1267-1277. [43] Wei J, Qian Y, Liu W, et al. Effects of particle composition and environmental parameters on catalytic hydrodechlorination of trichloroethylene by nanoscale bimetallic Ni-Fe[J]. Journal of Environmental Sciences, 2014,26(5):1162-1170. [44] Zhou Z, Ruan W, Huang H, et al. Fabrication and characterization of Fe/Ni nanoparticles supported by polystyrene resin for trichloroethylene degradation[J]. Chemical Engineering Journal, 2016,283:730-739. [45] Ruan X, Liu H, Wang J, et al. A new insight into the main mechanism of 2,4-dichlorophenol dechlorination by Fe/Ni nanoparticles[J]. The Science of the Total Environment, 2019,697(12): 133996. [46] Shin H J, Kim K K, Benayad A, et al. Efficient reduction of graphite oxide by sodium borohydride and its effect on electrical conductance[J]. Advanced Functional Materials, 2009,19(12):1987-1992. [47] Wang X, Huang S, Zhu L, et al. Correlation between the adsorption ability and reduction degree of graphene oxide and tuning of adsorption of phenolic compounds[J]. Carbon, 2014,69:101-112. [48] Xiao J, Lv W, Xie Z, et al. Environmentally friendly reduced graphene oxide as a broad-spectrum adsorbent for anionic and cationic dyes via π-π interactions[J]. Journal of Materials Chemistry A, 2016,4(31): 12126-12135. [49] 卫建军.纳米级Pd/Fe双金属对水中氯酚的催化脱氯研究[D]. 杭州:浙江大学, 2004. [50] Cheng R, Zhou W, Wang J L, et al. Dechlorination of pentachlorophenol using nanoscale Fe/Ni particles: role of nano-Ni and its size effect[J]. Journal of Hazardous materials, 2010,180(1-3): 79-85. [51] Zhang Z, Hu Y B, Ruan W, et al. Highly improved dechlorination of 2, 4-dichlorophenol in aqueous solution by Fe/Ni nanoparticles supported by polystyrene resin[J]. Chemosphere, 2021,266:128976.
