Abstract
Co3O4 is a promising Hg0 removal catalyst for industrial application. Operating temperature and low sulfur resistance are two of the main problems that hinder its industrial application in Hg0 removal. Herein, a metal-organic framework (Co-BDC) was introduced as a sacrificial template to obtain the catalyst nano-sized Co3O4@C by calcination. Part of the organic ligands is carbonized during the calcination. Carbon wrapped Co3O4 and reduced metal agglomeration. The optimal Hg0 removal temperature of the existing cobalt oxide catalysts was always around 150 °C, but H2-TPR showed that the oxygen atoms on the Co3O4@C were more active than those on Co3O4, causing the Hg0 removal temperature window of Co3O4@C to shift to lower temperatures. The Hg0 removal efficiency of Co3O4@C could reach almost 100% even at 25 °C. In the meanwhile, Co3O4@C also showed a strong SO2 resistance at ambient temperature. Experimental results and characterization proved that SO2 did not compete with Hg0 on the surface of Co3O4 at low temperatures. On the contrary, it participated in the oxidation of Hg0. This is a great improvement for Co3O4 catalyst in Hg0 removal. It reduces the restrictions on the application of Co3O4 in Hg0 removal. Co3O4@C shows considerable potential as an Hg0 removal catalyst.
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References
Bisson TM, Xu Z (2015) Potential hazards of brominated carbon sorbents for mercury emission control. Environ Sci Technol 49(4):2496–2502. https://doi.org/10.1021/es5052793
Busca G, Lietti L, Ramis G, Berti F (1998) Chemical and mechanistic aspects of the selective catalytic reduction of NOx by ammonia over oxide catalysts: a review. Appl Catal B Environ 18(1):1–36. https://doi.org/10.1016/S0926-3373(98)00040-X
Cao T, Li Z, Xiong Y, Yang Y, Xu S, Bisson T, Gupta R, Xu Z (2017) Silica-silver nanocomposites as regenerable sorbents for Hg(0) removal from flue gases. Environ Sci Technol 51(20):11909–11917. https://doi.org/10.1021/acs.est.7b01701
Chen W, Han B, Tian C, Liu X, Liang S, Deng H, Lin Z (2019) MOFs-derived ultrathin holey Co3O4 nanosheets for enhanced visible light CO2 reduction. Appl Catal B-Environ 244:996–1003. https://doi.org/10.1016/j.apcatb.2018.12.045
Chen W, Pei Y, Huang W, Qu Z, Hu X, Yan N (2016) Novel effective catalyst for elemental mercury removal from coal-fired flue gas and the mechanism investigation. Environ Sci Technol 50(5):2564–2572. https://doi.org/10.1021/acs.est.5b05564
Cheng T, Zhou X, Yang L, Wu H, Fan H (2020) Transformation and removal of ammonium sulfate aerosols and ammonia slip from selective catalytic reduction in wet flue gas desulfurization system. J Environ Sci 88:72–80. https://doi.org/10.1016/j.jes.2019.08.002
Dai E, Xu J, Qiu J, Liu S, Chen P, Liu Y (2017) Co@Carbon and Co 3 O4@Carbon nanocomposites derived from a single MOF for supercapacitors. Sci Rep 7(1):12588. https://doi.org/10.1038/s41598-017-12733-5
Hu Z, Li K, Wu X, Wang N, Li X, Li Q, Li L, Lv K (2019) Dramatic promotion of visible-light photoreactivity of TiO2 hollow microspheres towards NO oxidation by introduction of oxygen vacancy. Appl Catal B Environ 256:117860. https://doi.org/10.1016/j.apcatb.2019.117860
Ji G, George A, Skoulou V, Reed G, Millan M, Hooman K, Bhatia SK, Diniz Da Costa JC (2018) Investigation and simulation of the transport of gas containing mercury in microporous silica membranes. Chem Eng Sci 190:286–296. https://doi.org/10.1016/j.ces.2018.06.006
Jin R, Liu Y, Wu Z, Wang H, Gu T (2010) Low-temperature selective catalytic reduction of NO with NH(3) over Mn-Ce oxides supported on TiO2 and Al2O3: a comparative study. Chemosphere 78(9):1160–1166. https://doi.org/10.1016/j.chemosphere.2009.11.049
Li C, Chen T, Xu W, Lou X, Pan L, Chen Q, Hu B (2015) Mesoporous nanostructured Co3O4 derived from MOF template: a high-performance anode material for lithium-ion batteries. J Mater Chem A 3(10):5585–5591. https://doi.org/10.1039/c4ta06914e
Li H, Wu C-Y, Li Y, Zhang J (2011) CeO2-TiO2 catalysts for catalytic oxidation of elemental mercury in low-rank coal combustion flue gas. Environ Sci Technol 45(17):7394–7400. https://doi.org/10.1021/es2007808
Li H, Wu CY, Li Y, Li L, Zhao Y, Zhang J (2012) Role of flue gas components in mercury oxidation over TiO2 supported MnOx-CeO2 mixed-oxide at low temperature. J Hazard Mater 243:117–123. https://doi.org/10.1016/j.jhazmat.2012.10.007
Li J, Chen W, Zhao H, Zheng X, Wu L, Pan H, Zhu J, Chen Y, Lu J (2017a) Size-dependent catalytic activity over carbon-supported palladium nanoparticles in dehydrogenation of formic acid. J Catal 352:371–381. https://doi.org/10.1016/j.jcat.2017.06.007
Li Y, Duan Y, Wang H, Zhao S, Chen M, Liu M, Wei H (2017b) Effects of acidic gases on mercury adsorption by activated carbon in simulated oxy-fuel combustion flue gas. Energy Fuel 31(9):9745–9751. https://doi.org/10.1021/acs.energyfuels.7b01480
Li Y, Murphy PD, Wu C-Y, Powers KW, Bonzongo J-C J (2008) Development of silica/vanadia/titania catalysts for removal of elemental mercury from coal-combustion flue gas. Environ Sci Technol 42(14):5304–5309. https://doi.org/10.1021/es8000272
Liu C, Gong L, Dai R, Lu M, Sun T, Liu Q, Huang X, Huang Z (2017) Mesoporous Mn promoted Co3O4 oxides as an efficient and stable catalyst for low temperature oxidation of CO. Solid State Sci 71:69–74. https://doi.org/10.1016/j.solidstatesciences.2017.07.006
Liu Y (2008) Comment on "Impact of Sulfur Oxides on Mercury Capture by Activated Carbon". Environ Sci Technol 42(3):970–971. https://doi.org/10.1021/es7021347
Liu Y, Wang Y, Wang H, Wu Z (2011) Catalytic oxidation of gas-phase mercury over Co/TiO2 catalysts prepared by sol-gel method. Catal Commun 12(14):1291–1294. https://doi.org/10.1016/j.catcom.2011.04.017
Machida M, Murata Y, Kishikawa K, Zhang D, Ikeue K (2008) On the reasons for high activity of CeO2 catalyst for soot oxidation. Chem Mater 20(13):4489–4494. https://doi.org/10.1021/cm800832w
Mochida I, Korai Y, Shirahama M, Kawano S, Hada T, Seo Y, Yoshikawa M, Yasutake A (2000) Removal of SOx and NOx over activated carbon fibers. Carbon 38(2):227–239. https://doi.org/10.1016/s0008-6223(99)00179-7
Pacyna EG, Pacyna JM, Steenhuisen F, Wilson S (2006) Global anthropogenic mercury emission inventory for 2000. Atmos Environ 40(22):4048–4063. https://doi.org/10.1016/j.atmosenv.2006.03.041
Pavlish JH, Sondreal EA, Mann MD, Olson ES, Galbreath KC, Laudal DL, Benson SA (2003) Status review of mercury control options for coal-fired power plants. Fuel Process Technol 82(2-3):89–165. https://doi.org/10.1016/s0378-3820(03)00059-6
Peng H-J, Hao G-X, Chu Z-H, Lin J, Lin X-M, Cai Y-P (2017) Mesoporous Mn3O4/C microspheres fabricated from MOF template as advanced lithium-ion battery anode. Cryst Growth Des 17(11):5881–5886. https://doi.org/10.1021/acs.cgd.7b00978
Presto AA, Granite EJ (2006) Survey of catalysts for oxidation of mercury in flue gas. Environ Sci Technol 40(18):5601–5609. https://doi.org/10.1021/es060504i
Shekhah O, Liu J, Fischer RA, Woll C (2011) MOF thin films: existing and future applications. Chem Soc Rev 40(2):1081–1106. https://doi.org/10.1039/c0cs00147c
Tao K, Han X, Cheng Q, Yang Y, Yang Z, Ma Q, Han L (2018) A zinc cobalt sulfide nanosheet array derived from a 2D bimetallic metal-organic frameworks for high-performance supercapacitors. Chemistry 24(48):12584–12591. https://doi.org/10.1002/chem.201800960
Wang T, Li C, Zhao L, Zhang J, Li S, Zeng G (2017) The catalytic performance and characterization of ZrO2 support modification on CuO-CeO2/TiO2 catalyst for the simultaneous removal of Hg-0 and NO. Appl Surf Sci 400:227–237. https://doi.org/10.1016/j.apsusc.2016.12.192
Wei W, Chen W, Ivey DG (2008) Rock salt-spinel structural transformation in anodically electrodeposited Mn-Co-O nanocrystals. Chem Mater 20(5):1941–1947. https://doi.org/10.1021/cm703464p
Xu HM, Qu Z, Zhao SJ, Mei J, Quan FQ, Yan NQ (2015) Different crystal-forms of one-dimensional MnO2 nanomaterials for the catalytic oxidation and adsorption of elemental mercury. J Hazard Mater 299:86–93. https://doi.org/10.1016/j.jhazmat.2015.06.012
Xu W, Hussain A, Liu Y (2018) A review on modification methods of adsorbents for elemental mercury from flue gas. Chem Eng J 346:692–711. https://doi.org/10.1016/j.cej.2018.03.049
Yang J, Zhao Y, Chang L, Zhang J, Zheng C (2015) Mercury adsorption and oxidation over cobalt oxide loaded magnetospheres catalyst from fly ash in oxyfuel combustion flue gas. Environ Sci Technol 49(13):8210–8218. https://doi.org/10.1021/acs.est.5b01029
Yang J, Zhao Y, Zhang J, Zheng C (2014) Regenerable cobalt oxide loaded magnetosphere catalyst from fly ash for mercury removal in coal combustion flue gas. Environ Sci Technol 48(24):14837–14843. https://doi.org/10.1021/es504419v
Yang S, Guo Y, Yan N, Qu Z, Xie J, Yang C, Jia J (2011) Capture of gaseous elemental mercury from flue gas using a magnetic and sulfur poisoning resistant sorbent Mn/gamma-Fe2O3 at lower temperatures. J Hazard Mater 186(1):508–515. https://doi.org/10.1016/j.jhazmat.2010.11.034
Yang W, Chen H, Han X, Ding S, Shan Y, Liu YX (2020) Preparation of magnetic Co-Fe modified porous carbon from agricultural wastes by microwave and steam activation for mercury removal. J Hazard Mater 381:10. https://doi.org/10.1016/j.jhazmat.2019.120981
Zhang A, Zheng W, Song J, Hu S, Liu Z, Xiang J (2014) Cobalt manganese oxides modified titania catalysts for oxidation of elemental mercury at low flue gas temperature. Chem Eng J 236:29–38. https://doi.org/10.1016/j.cej.2013.09.060
Zhang H, Wang T, Zhang Y, Wang J, Sun B, Pan W-P (2020a) A review on adsorbent/catalyst application for mercury removal in flue gas: effect of sulphur oxides (SO2, SO3). J Clean Prod 276:124220. https://doi.org/10.1016/j.jclepro.2020.124220
Zhang L, Li L, Cao Y, Yao X, Ge C, Gao F, Deng Y, Tang C, Dong L (2015) Getting insight into the influence of SO2 on TiO2/CeO2 for the selective catalytic reduction of NO by NH3. Appl Catal B-Environ 165:589–598. https://doi.org/10.1016/j.apcatb.2014.10.029
Zhang LX, Feng LP, Li P, Chen X, Jiang JT, Zhang S, Zhang CX, Zhang AC, Chen GF, Wang H (2020b) Direct Z-scheme photocatalyst of hollow CoSx@CdS polyhedron constructed by ZIF-67-templated one-pot solvothermal route: a signal-on photoelectrochemical sensor for mercury (II). Chem Eng J 395:14. https://doi.org/10.1016/j.cej.2020.125072
Zhang X, Shen B, Shen F, Zhang X, Si M, Yuan P (2017a) The behavior of the manganese-cerium loaded metal-organic framework in elemental mercury and NO removal from flue gas. Chem Eng J 326:551–560. https://doi.org/10.1016/j.cej.2017.05.128
Zhang X, Wang J, Tan B, Li Z, Cui Y, He G (2017b) Ce-Co catalyst with high surface area and uniform mesoporous channels prepared by template method for Hg-0 oxidation. Catal Commun 98:5–8. https://doi.org/10.1016/j.catcom.2017.04.024
Zhang X, Zhang H, Zhu H, Li C, Zhang N, Bao J, He G (2019a) Co3O4 nanorods with a great amount of oxygen vacancies for highly efficient hg0 oxidation from coal combustion flue gas. Energy Fuel 33(7):6552–6561. https://doi.org/10.1021/acs.energyfuels.9b00765
Zhang X, Zhang H, Zhu H, Li C, Zhang N, Bao J, He G (2019b) Co3O4 nanorods with a great amount of oxygen vacancies for highly efficient Hg-0 oxidation from coal combustion flue gas. Energy Fuel 33(7):6552–6561. https://doi.org/10.1021/acs.energyfuels.9b00765
Zhou J, Cao L, Wang Q, Tariq M, Xue Y, Zhou Z, Sun W, Yang J (2019) Enhanced Hg0 removal via α-MnO2 anchored to MIL-96(Al). Appl Surf Sci 483:252–259. https://doi.org/10.1016/j.apsusc.2019.03.261
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This research is based on the work supported by the National Natural Science Foundation of China (Project No.51778229, 21307032) and the Fundamental Research Funds for the Central Universities (Project No. JKB012015019).
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All authors (Jiacheng Zhou, Qicheng Shen, Jie Yang, Muhammad Tariq, Wei Sun, Limei Cao, and Ji Yang) read and approved the final manuscript.
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Zhou, ., Shen, Q., Yang, J. et al. A novel nano-sized Co3O4@C catalyst derived from Co-MOF template for efficient Hg0 removal at low temperatures with outstanding SO2 resistance. Environ Sci Pollut Res 28, 65487–65498 (2021). https://doi.org/10.1007/s11356-021-15663-y
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DOI: https://doi.org/10.1007/s11356-021-15663-y