前驱体转化法可控制备γ-二氧化锰及其催化燃烧甲苯性能

doi:10.19964/j.issn.1006-4990.2021-0696

Abstract

Abstract:

Three groups of γ-MnO₂ catalysts（Mn-N，Mn-S，Mn-A） were prepared by disproportionation reaction between Mn₃O₄ and nitric acid，sulfuric acid，and acetic acid，respectively.The effect of different acid on the structure and morphology of the products was studied.The physical and chemical properties of the products were systematically analyzed by X-ray diffraction（XRD），scanning electron microscopy（FE-SEM），transmission electron microscopy（HR-TEM），nitrogen adsorption desorption，X-ray photoelectron spectroscopy（XPS），hydrogen temperature programmed reduction（H₂-TPR） and oxygen temperature programmed desorption（O₂-TPD）.And toluene catalytic combustion was used as a probe reaction to evaluate the activity of γ-MnO₂ catalyst.The results showed that the catalyst Mn-N treated with nitric acid had the best catalytic combustion activity for toluene.Under the condition of mass space velocity of 40 000 mL/（g·h），the ignition temperature T₁₀（corresponding conversion of 10%） was 190 ℃，and the complete combustion temperature T₉₀（corresponding conversion of 90%） was 229 ℃.This may be related to its large specific surface area，high content of Mn（Ⅲ） and adsorbed oxygen species，good reducibility and lattice oxygen flow ability.In addition，Mn-N could still maintain good catalytic activity after continuous stability experiments for 30 h.

Key words: precursor conversion, Mn₃O₄, γ-MnO₂, toluene, catalytic combustion

CLC Number:

TQ137.12

TANG Shichang,CHENG Gao,LIU Qi,YE Fan,SUN Ming,YU Lin. Controllable preparation of γ-MnO₂ by precursor conversion method and its catalytic combustion performance of toluene[J]. Inorganic Chemicals Industry, 2022, 54(6): 134-141.

Figures/Tables 10

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Table 1

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References 36

1	ZOU Weixin， GAO Bin， OK Y S，et al.Integrated adsorption and photocatalytic degradation of volatile organic compounds（VOCs） using carbon⁃based nanocomposites：A critical review［J］.Chemosphere，2019，218：845-859.
2	BAI Bingyang， QIAO Qi， LI Junhua，et al.Progress in research on catalysts for catalytic oxidation of formaldehyde［J］.Chinese Journal of Catalysis，2016，37（1）：102-122.
3	ZHANG Ling， PENG Yuexin， ZHANG Juan，et al.Adsorptive and catalytic properties in the removal of volatile organic compounds over zeolite⁃based materials［J］.Chinese Journal of Catalysis，2016，37（6）：800-809.
4	LI Liping， PAN Yinzhen， CHEN Lijuan，et al.One⁃dimensional α-MnO₂：Trapping chemistry of tunnel structures，structural stability，and magnetic transitions［J］.Journal of Solid State Chemistry，2007，180（10）：2896-2904.
5	WANG Jian， ZHAO Hainan， SONG Jianfei，et al.Structure⁃activity relationship of manganese oxide catalysts for the catalytic oxidation of（chloro）-VOCs［J］.Catalysts，2019，9（9）.Doi：10.3390/ catal9090726 . doi: 10.3390/ catal9090726
6	BOYJOO Y， ROCHARD G， GIRAUDON J M，et al.Mesoporous MnO₂ hollow spheres for enhanced catalytic oxidation of formaldehyde［J］.Sustainable Materials and Technologies，2019，20.Doi：10.1016/j.susmat.2018.e00091 . doi: 10.1016/j.susmat.2018.e00091
7	WENG Xiaole， LONG Yu， WANG Wanglong，et al.Structural effect and reaction mechanism of MnO₂ catalysts in the catalytic oxidation of chlorinated aromatics［J］.Chinese Journal of Catalysis，2019，40（5）：638-646.
8	YANG Yang， HUANG Jun， WANG Siwen，et al.Catalytic removal of gaseous unintentional POPs on manganese oxide octahedral molecular sieves［J］.Applied Catalysis B：Environmental，2013，142-143：568-578.
9	JIANG Yong， CHENG Gao， YANG Runnong，et al.Influence of preparation temperature and acid treatment on the catalytic activity of MnO₂ ［J］.Journal of Solid State Chemistry，2019，272：173- 181
10	WANG Jinlong， LI Jinge， JIANG Chuanjia，et al.The effect of manganese vacancy in birnessite⁃type MnO₂ on room⁃temperature oxidation of formaldehyde in air［J］.Applied Catalysis B：Environmental，2017，204：147-155.
11	YAMAGUCHI Y， AONO R， HAYASHI E，et al.Template⁃free
	synthesis of mesoporous β-MnO 2 nanoparticles：Structure，formation mechanism，and catalytic properties［J］.ACS Applied Materials & Interfaces，2020，12（32）：36004-36013.
12	SI Wenzhe， WANG Yu， PENG Yue，et al.Selective dissolution of A-site cations in ABO₃ perovskites：A new path to high⁃performance catalysts［J］.Angewandte Chemie International Edition，2015，54（27）：7954-7957.
13	ZENG Xiaohong， CHENG Gao， LIU Qi，et al.Novel ordered mesoporous γ-MnO₂ catalyst for high⁃performance catalytic oxidation of toluene and o-xylene［J］.Industrial & Engineering Chemistry Research，2019，58（31）：13926-13934.
14	SI Wenzhe， WANG Yu， PENG Yue，et al.A high⁃efficiency ga⁃ mma-MnO 2 -like catalyst in toluene combustion［J］.Chemical Co⁃ mmunications，2015，51（81）：14977-14980.
15	DESAI M A， VEDPATHAK A S， BHAPKAR A R，et al.An investigation of chemical and electrochemical conversion of SILAR grown Mn₃O₄ into MnO₂ thin films［J］.Journal of Environmental Management，2021，299.Doi：10.1016/j.jenvman.2021.113564 . doi: 10.1016/j.jenvman.2021.113564
16	PAN Jia hong， HUANG Qizhao， KOH Z Y，et al.Scalable synthesis of urchin- and flowerlike hierarchical NiO microspheres and their electrochemical property for lithium storage［J］.ACS Applied Materials & Interfaces，2013，5（13）：6292-6299.
17	Yue LYU， LI Caiting， DU Xueyu，et al.Catalytic oxidation of toluene over MnO₂ catalysts with different Mn（Ⅱ） precursors and the study of reaction pathway［J］.Fuel，2020，262.Doi：10.1016/j.fuel.2019.116610 . doi: 10.1016/j.fuel.2019.116610
18	FENG Chao， XIONG Gaoyan， LI Yaping，et al.High⁃precision synthesis of α-MnO₂ nanowires with controllable crystal facets for propane oxidation［J］.CrystEngComm，2021，23（43）：7602-7614.
19	GU Wenxiu， LI Chenqi， QIU Jianhao，et al.Facile fabrication of flower⁃like MnO₂ hollow microspheres as high⁃performance catalysts for toluene oxidation［J］.Journal of Hazardous Materials，2021，408.Doi：10.1016/j.jhazmat.2020.124458 . doi: 10.1016/j.jhazmat.2020.124458
20	SHI Fengjuan， WANG Fang， DAI Hongxing，et al.Rod-，flower-，and dumbbell⁃like MnO₂：Highly active catalysts for the combustion of toluene［J］.Applied Catalysis A：General，2012，433-434：206-213.
21	LI Luming， LUO Jingjie， LIU Yuefeng，et al.Self⁃propagated flaming synthesis of highly active layered CuO-δ-MnO₂ hybrid composites for catalytic total oxidation of toluene pollutant［J］.ACS Applied Materials & Interfaces，2017，9（26）：21798-21808.
22	ZHANG Chuanhui， HUANG He， LI Genqin，et al.Zeolitic acidity as a promoter for the catalytic oxidation of toluene over MnO _x /HZSM-5 catalysts［J］.Catalysis Today，2019，327：374-381.
23	LI Xinwei， DAI Hongxing， DENG Jiguang，et al.In situ PMMA-templating preparation and excellent catalytic performance of Co₃O₄/3DOM La_0.6Sr_0.4CoO₃ for toluene combustion［J］.Applied Catalysis A：General，2013，458：11-20.
24	ZHAO Jiuhu， TANG Zhicheng， DONG Fang，et al.Controlled porous hollow Co₃O₄ polyhedral nanocages derived from metal⁃organic frameworks（MOFs） for toluene catalytic oxidation［J］.Molecular Catalysis，2019，463：77-86.
25	DU Yucheng， MENG Qi， WANG Jinshu，et al.Three⁃dimensional mesoporous manganese oxides and cobalt oxides：High⁃efficiency catalysts for the removal of toluene and carbon monoxide［J］.Microporous and Mesoporous Materials，2012，162：199-206.
26	XIE Shaohua， DAI Hongxing， DENG Jiguang，et al.Preparation and high catalytic performance of Au/3DOM Mn₂O₃ for the oxidation of carbon monoxide and toluene［J］.Journal of Hazardous Materials，2014，279：392-401.
27	XIE Shaohua， DAI Hongxing， DENG Jiguang，et al.Au/3DOM Co₃O₄：Highly active nanocatalysts for the oxidation of carbon mo⁃
	noxide and toluene［J］.Nanoscale，2013，5（22）：11207-11219.
28	CHAN Z M， KITCHAEV D A， NELSON WEKER J，et al.Electrochemical trapping of metastable Mn³⁺ions for activation of MnO₂ oxygen evolution catalysts［J］.Proceedings of the National Academy of Sciences of the United States of America，2018，115（23）：E5261-E5268.
29	DONG Cui， QU Zhenping， JIANG Xiao，et al.Tuning oxygen vacancy concentration of MnO₂ through metal doping for improved toluene oxidation［J］.Journal of Hazardous Materials，2020，391.Doi：10.1016/j.jhazmat.2020.122181 . doi: 10.1016/j.jhazmat.2020.122181
30	JIA Jingbo， ZHANG Pengyi， CHEN Long.Catalytic decomposition of gaseous ozone over manganese dioxides with different crys⁃
	tal structures［J］.Applied Catalysis B：Environmental，2016，189：210-218.
31	GENUINO H C， MENG Yongtao， HORVATH D T，et al.Enhancement of catalytic activities of octahedral molecular sieve manganese oxide for total and preferential CO oxidation through vanadium ion framework substitution［J］.ChemCatChem，2013，5（8）：2306-2317.
32	SUN Liang， CAO Qingqing， HU Bingqing，et al.Synthesis，characterization and catalytic activities of vanadium⁃cryptomelane man⁃
	manganese oxides in low⁃temperature NO reduction with NH 3［J］.Applied Catalysis A：General，2011，393（1/2）：323-330.
33	MO Shengpeng， ZHANG Qi， LI Jiaqi，et al.Highly efficient mesoporous MnO₂ catalysts for the total toluene oxidation：Oxygen⁃Vacancy defect engineering and involved intermediates using in situDRIFTS［J］.Applied Catalysis B：Environmental，2020，264.Doi：10.1016/j.apcatb.2019.118464 . doi: 10.1016/j.apcatb.2019.118464
34	ZHANG Runduo， VILLANUEVA A， ALAMDARI H，et al.Reduction of NO by CO over nanoscale LaCo_1- _x Cu _x O₃ and LaMn_1- _x Cu _x O₃ perovskites［J］.Journal of Molecular Catalysis A：Chemical，2006，258（1/2）：22-34.
35	HUANG Na， QU Zhenping， DONG Cui，et al.Superior performance of α@β-MnO₂ for the toluene oxidation：Active interface and oxygen vacancy［J］.Applied Catalysis A：General，2018，560：
	195-205.
36	孙梦婷，黄碧纯，马杰文，等.二氧化锰在低温NH₃-SCR催化反应上的形貌效应［J］.物理化学学报，2016，32（6）：1501-1510.
	SUN Mengting， HUANG Bichun， MA Jiewen，et al.Morphological effects of manganese dioxide on catalytic reactions for low⁃temperature NH₃-SCR［J］.Acta Physico-Chimica Sinica，2016，32（6）：1501-1510.

样品	比表面积/ （m²·g^-1）	平均孔径/ nm	催化燃烧甲苯活性		n（Mn³⁺）/ n（Mn⁴⁺）	n（O_A）/ n（O_L）	H₂-TPR 峰/℃	O₂-TPD 峰/℃
样品	比表面积/ （m²·g^-1）	平均孔径/ nm	T₁₀/℃	T₉₀/℃	n（Mn³⁺）/ n（Mn⁴⁺）	n（O_A）/ n（O_L）	H₂-TPR 峰/℃	O₂-TPD 峰/℃
Mn-N	155.2	17.36	190	229	1.70	1.15	217	441
Mn-S	82.0	17.50	203	237	1.58	0.96	240	464
Mn-A	115.2	23.56	211	258	1.13	0.77	248	487

样品	反应条件		催化燃烧甲苯活性
样品	甲苯体积分数/10^-6	空速/ （mL·g^-1·h^-1）	T₁₀/℃	T₉₀/℃
花状ε-MnO₂^［19］	1 000	40 000	217	280
棒状α-MnO₂^［20］	1 000	21 000	220	250
Mn10Cu1-S^［21］	1 000	15 000	210	258
10%MnO _x /HZSM-5-25^［22］	1 000	24 000	220	261
2%Co₃O₄/3DOM LSCO^［23］	1 000	21 000	190	243
Co₃O₄-400^［24］	1 000	20 000	218	259
Co₃O₄-KIT-6^［25］	1 000	15 000	203	233
5.8%Au/3DOM Mn₂O₃^［26］	1 000	40 000	211	244
6.5Au/3DOM Co₃O₄^［27］	1 000	40 000	215	256
Mn-N（制备样品）	1 000	40 000	190	229

[1]	LI Yongheng, MI Xiaotong, ZHANG Peipei. Synthesis of holycrystalline nano-ZSM-5 aggregate and its application in methylation of toluene [J]. Inorganic Chemicals Industry, 2024, 56(5): 135-140.
[2]	Peng Xiaowei,Wang Yinbin,Zang Jiazhong,Yu Haibin. Research on preparation of metal modified catalysts and catalytic performances of methanol aromatization [J]. Inorganic Chemicals Industry, 2021, 53(9): 104-108.
[3]	Li Xiaoguo, Li Yongheng, Hou Zhanggui, Han Guodong, Xiao Jiawang, Gao Jinping, Chang Yang. Study on pilot catalytic performance of the modified catalyst for alkylation of toluene with methanol to p-xylene [J]. Inorganic Chemicals Industry, 2021, 53(3): 97-101.
[4]	Hou Zhanggui,Zhu Qianqian,Li Xiaoguo,Li Yongheng,Chang Yang,Zhang Anfeng,Guo Xinwen. Preparation of modificated micro-mesoporous ZSM-5 molecular sieve catalyst and its catalytic performance for alkylation of toluene with methanol [J]. Inorganic Chemicals Industry, 2020, 52(9): 96-99.
[5]	Luo Chengguo,Xiao Jun,Fan Guangxin. Current situation and development of precursors for LiMn₂O₄ cathode used in lithium ion batteries [J]. Inorganic Chemicals Industry, 2020, 52(1): 26-29.
[6]	LI San-Xi, SONG Shu-Dong, WANG Song, XIE Mei-Zhu. Direct conversion preparation of magnesium hydroxide induced by sodium p-toluene sulfonate [J]. INORGANICCHEMICALSINDUSTRY, 2016, 48(5): 20-.
[7]	LI Yong-Feng, XIAO Yue, WEN Wu, GAO Min, YU Qian, YU Lin. Characterization of Pd/FeCrAl fiber monolithic catalysts and catalytic combustion properties of toluene thereof [J]. INORGANICCHEMICALSINDUSTRY, 2014, 46(12): 75-.
[8]	FAN Jing-Xin, JING Wei-Dong, YU Hai-Bin, ZANG Jia-Zhong, XING Shu-Jian. Research progress in catalysts for selective alkylation of toluene and methanol [J]. INORGANICCHEMICALSINDUSTRY, 2013, 45(6): 62-.
[9]	WANG Peng-Cheng, LIU Song, LIU Meng-Xi. Study on preparation and dispersivity of monodisperse silica nanoparticles [J]. INORGANICCHEMICALSINDUSTRY, 2011, 43(2): 40-.

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Controllable preparation of γ-MnO₂ by precursor conversion method and its catalytic combustion performance of toluene

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Controllable preparation of γ-MnO2 by precursor conversion method and its catalytic combustion performance of toluene