Abstract
Hollow microspheres MnCo2O4 and CoMn2O4 have been synthesized by a facile solvothermal route followed by pyrolysis of the carbonate counterparts and carbon microspheres, using carbon microspheres as the template. The NH3-selective catalytic reduction reaction was used to test the catalytic activity. The obtained hollow microspheres are composed of numerous primary particles with sizes of tens of nanometers, giving a porous shell. The obtained CoMn2O4 microsphere shows better low-temperature catalytic activity and N2 selectivity than MnCo2O4 microsphere in the NH3-selective catalytic reduction reaction. The X-ray photoelectron spectroscopy results demonstrate that CoMn2O4 microsphere has a relatively higher number content of Mn3+ and chemisorbed oxygen species. The temperature-programmed desorption by ammonia and in situ diffuse reflectance infrared Fourier transform spectroscopy results indicate that the CoMn2O4 microsphere possesses stronger Lewis acid strength than the MnCo2O4 microsphere. Additionally, the CoMn2O4 microsphere also presented outstanding stability, H2O resistance and SO2 tolerance.
Graphical Abstract
The NH3-SCR reaction mechanism is proposed that NH3(g) is adsorbed on the surface of Lewis acid sites and Brønsted acid sites in the shape of NH4 + ions and gaseous NH3. Besides, the adsorption of NO could exist in the form of gaseous or oxide ions NO2 − on the surface of catalysts.The adsorbed NH3 species could react with NO2 − species easily to produce NH4NO2, which subsequently to produce the innocuous N2 and H2O.
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References
Liu ZM, Lua YN, Yua L, Ma LL, Zheng LR, Zhang J, Hu TD (2016) Appl Catal B: Environ 188:189–197
Tang CJ, Zhang HL, Dong L (2016) Catal Sci Technol 6:1248–1264
Liu F, Asakurab K, He H, Liu Y, Shan W, Shi X, Zhang C (2011) Catal Today 164:520–530
Gao X, Liu S, Zhang Y, Luo Z, Cen K (2011) J Hazard Mater 188:58–64
Chang HZ, Jong MT, Wang CZ, Qu RY, Du Y, Li JH, Hao JM (2013) Environ Sci Technol 47:11692–11699
Maqbool MS, Pullur AK, Ha HP (2014) Appl Catal B: Environ 152-153:28–35
Hea YY, Forda ME, Zhu MH, Liu QC, Wu ZL, Wach IE (2016) Appl Catal B: Environ 188:123–133
Wu Z, Jiang B, Liu Y (2008) Appl Catal B 79:347–354
Chen L, Li JH, Ge M (2010) Environ Sci Technol 44:9590–9596
Liu F, He H, Zhang C, Shan W, Shi X (2011) Catal Today 175:18–26
Li X, Li JH, Peng Y, Chang HZ, Zhang T, Zhao S, Si WZ, Hao JM (2016) Appl Catal B 184:246–257
He CH, Kohler K (2011) J Phys Chem C 115:1248–1254
Bin F, Song CL, Lv G, Song J, Cao XF, Pang HT, Wang KP (2012) J Phys Chem C 116:26262–26274
Wallin M, Forser S, Thormahlen P, Skoglundh M (2004) Ind Eng Chem Res 43:7723–7731
Pietrzyk P, Dujardin C, Marek KG, Granger P, Sojkaa Z (2012) Phys Chem Chem Phys 14:2203–2215
Shu Z, Huang WM, Hua ZL, Zhang LX, Cui XZ, Chen Y, Chen HR, Wei CY, Wang YX, Fan XQ, Yao HL, He DN, Shi JL (2013) J Mater Chem A 1:10218–10227
Mihaylov M, Hadjiivanov K (2004) Chem Commun 5:2200–2209
Fang C, Zhang DS, Cai SJ, Zhang L, Huang L, Li HR, Maitarad P, Shi LY, Gao RH, Zhang JP (2013) Nanoscale 5:9199–9207
Chang HZ, Chen XY, Li JH, Ma L, Wang CZ, Liu CX, Schwank JW, Hao JM (2013) Environ Sci Technol 47:5294–5301
Tian W, Yang HS, Fan XY, Zhang XB (2011) J Hazard Mater 188:105–109
Wan Y, Zhao W, Tang Y, Li L, Wang H, Cui Y, Gu J, Li Y, Shi J (2014) Appl Catal B 148-149:114–121
Meng B, Zhao ZB, Wang XZ, Liang JJ, Qiu JS (2013) Appl Catal B: Environ 129:491–500
Yang S, Wanga C, Li J, Yan N, Ma L, Chang H (2013) Appl Catal B 110:71–79
Zhang L, Zhang DS, Zhang JP, Cai SX, Fang C, Huang L, Li HR, Gao RH, Shi LY (2013) Nanoscale 5:9821–9829
Zhang DS, Zhang L, Fang C, Gao R, Qian YL, Shi LY, Zhang JP (2013) RSC Adv 3:8811–8819
Aguilera DA, Perez A, Molina R, Moreno S (2011) Appl Catal B: Environ 104:144–150
Shi C, Wang Y, Zhu A, Chen BB, Au C (2012) Catal Commun 28:18–22
Zhang L, Shi LY, Huang L, Zhang JP, Gao RH, Zhang DS (2014) ACS Catal 4:1753–1763
Gao RH, Zhang DS, Maitarad P, Shi LY, Rungrotmongkol T, Li HR, Zhang JP, Cao WG (2013) J Phys Chem C 117:10502–10511
Li J, Wang J, Liang X, Zhang Z, Liu H, Qian Y, Xiong S (2014) ACS Appl Mater Interfaces 6:24–31
Sun XM, Li YD (2004) Angew Chem Int Ed 43:597–604
Wang LZ, Tang FQ, Ozawa K, Chen ZG, Mukherj A, Zhu YC, Zou J, Cheng HM, Lu GQ (2009) Angew Chem Int Ed 48:7048–7056
Zhou L, Zhao DY, Lou XW (2012) Adv Mater 24:745–748
Li J, Xiong S, Li X, Qian Y (2013) Nanoscale 5:2045–2053
Tang XF, Li JH, Sun L, Hao JM (2010) Appl Catal B: Environ 99:156–162
Shi C, Wang Y, Zhu A, Chen B, Au C (2012) Catal Commun 28:18–26
Aguilera DA, Perez A, Molina R, Moreno S (2011) Appl Catal B: Environ 104:144–152
Yang SJ, Wang CZ, Li JH, Yan NQ, Ma L, Chang HZ (2011) Appl Catal B: Environ 110:71–80
Chen L, Li J, Ge M (2010) Environ Sci Technol 44:9590–9598
Qi GS, Yang RT (2004) Phys Chem B 108:15738–15746
Liu F, He H (2004) Catal Today 153:70–76
Si Z, Weng D, Wu X, Li J, Li G (2010) J Catal 271:43–51
Gu T, Jin R, Liu Y, Liu H, Weng X, Wu Z (2013) Appl Catal B: Environ 129:30–38
Casapu M, Kröcher O, Mehring M, Nachtegaal M, Borca C, Harfouche M, Grolimund D (2010) J Phys Chem C 114:9791
Hadjiivanov KI (2004) Catal Rev 42:71–79
Yao X, Zhang L, Li L, Liu L, Cao Y, Dong X, Gao F, Deng Y, Tang C, Chen Z, Dong L, Chen Y (2014) Appl Catal B: Environ 150-151:315–322
Kijlstra WS, Brands DS, Smit HI, Poels EK, Bliek A (1997) J Catal 171:219–227
Wang LZ, Tang FQ, Ozawa K, Chen ZG, Mukherj A, Zhu YC, Zou J, Cheng HM, Lu GQ (2009) Angew Chem Int Ed 48:7048–7051
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This work was supported by the National Natural Science Foundtion of China (Grant No. 21377061, 81270041), Independent Innovation fund of Tianjin University (2015XRG-0020 and 2016XJ-0006), and by Natural Science Foundation of Tianjin (Grant No. 15JCYBJC48400, 16YFZCSF00300 and 15JCZDJC41200).
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Li, Y., Li, Y., Shi, Q. et al. Novel hollow microspheres MnxCo3−xO4 (x = 1, 2) with remarkable performance for low-temperature selective catalytic reduction of NO with NH3 . J Sol-Gel Sci Technol 81, 576–585 (2017). https://doi.org/10.1007/s10971-016-4208-8
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DOI: https://doi.org/10.1007/s10971-016-4208-8