双金属有机骨架材料衍生CuO-Cu1.5Mn1.5O4复合氧化物的丙烷催化燃烧性能

冯超; 熊高燕; 汪云霞; 潘原; 柳云骐

doi:10.13205/j.hjgc.202208009

双金属有机骨架材料衍生CuO-Cu_1.5Mn_1.5O₄复合氧化物的丙烷催化燃烧性能

doi: 10.13205/j.hjgc.202208009

中国石油大学(华东) 化学工程学院, 山东青岛 266580

基金项目:

国家自然科学基金(21878334)

山东省泰山学者青年专家人才项目(tsqn201909065)

详细信息

作者简介:
冯超(1990-),男,博士,主要研究方向为VOCs污染控制。fch_upc@163.com

通讯作者:
柳云骐(1963-),男,博士,教授,主要研究方向为重质油加氢,大气污染物控制。liuyq@upc.edu.cn

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出版历程
- 收稿日期: 2021-08-24
- 刊出日期: 2022-11-08

SYNTHESIS OF CuO-Cu_1.5Mn_1.5O₄ COMPOSITE OXIDE BY USING A BIMETALLIC ORGANIC FRAMEWORK FOR CATALYTIC PROPANE TOTAL OXIDATION

College of Chemical Engineering, China University of Petroleum (East China), Qingdao 266580, China

摘要

摘要: 采用气相辅助的离子置换法,合成了Cu、Mn双金属有机骨架(MOF)材料,通过控制煅烧条件制备了一系列CuO-Cu_1.5Mn_1.5O₄复合氧化物,研究了不同n(Mn)/n(Cu)对丙烷催化燃烧性能的影响。结果表明:随着n(Mn)/n(Cu)提高,CuO-Cu_1.5Mn_1.5O₄催化丙烷燃烧能力增强,当n(Mn)/n(Cu)为31∶69时,催化剂对丙烷的完全燃烧温度(T₉₀)仅为309.8 ℃,催化活性远高于CuO和Mn₂O₃。表征和密度泛函理论(DFT)计算结果表明,由于Mn和Cu的相互作用,复合氧化物表面具有更高的n(Mn⁴⁺)/n(Mn³⁺)和n(Cu⁺)/n(Cu²⁺),从而增强了催化剂的低温还原性能。并且n(Cu⁺)/n(Cu²⁺)提高导致催化剂中氧空位浓度升高,更容易吸附活化O₂、丙烷分子,增强了催化剂的丙烷燃烧性能。
- CuO-Cu_1.5Mn_1.5O₄复合氧化物 /
- 丙烷催化燃烧 /
- 氧化还原性能 /
- MOF材料 /
- 协同作用
Abstract: In the paper, Cu and Mn bimetallic organic framework materials were prepared using the gas-assisted ion replacement method. A series of CuO-Cu_1.5Mn_1.5O₄ composite oxides were prepared through controlled calcination, and the effect of various n(Mn)/n(Cu) on the catalytic performance of propane total oxidation was studied. The results revealed that with an increase in the n(Mn)/n(Cu), CuO-Cu_1.5Mn_1.5O₄ catalysts showed enhanced propane total oxidation catalytic activities. When n(Mn)/n(Cu) was 31∶69, the complete combustion temperature (T₉₀) of propane was just 309.8 ℃, signifying that the activity was much higher than that of CuO and Mn₂O₃. The experimental and density functional theory (DFT) calculation results revealed that the synergetic effect of Mn and Cu increased the n(Mn⁴⁺)/n(Mn³⁺) and n(Cu⁺)/n(Cu²⁺) on the surface, which enhanced the redox ability at low-temperature. Meanwhile, the increase of n(Cu⁺)/n(Cu²⁺) led to a higher concentration of oxygen vacancies, and made it easier to adsorb and activate oxygen and propane molecules on the surface, thereby boosted the propane catalytic oxidation performance.
- CuO-Cu_1.5Mn_1.5O₄ composite oxides /
- catalytic propane oxidation /
- redox properties /
- MOF material /
- syneretic effect

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参考文献(27)

[1]	WU E,FENG X,ZHENG Y,et al.Inverse coprecipitation directed porous core-shell Mn-Co-O catalyst for efficient low temperature propane oxidation[J].ACS Sustainable Chemistry & Engineering,2020,8(14):5787-5798.
[2]	FEI J B,CUI Y,YAN X H,et al.Controlled preparation of MnO₂ hierarchical hollow nanostructures and their application in water treatment[J].Advanced Materials,2008,20(3):452-456.
[3]	LIAO W M,ZHAO P P,CEN B H,et al.Co-Cr-O mixed oxides for low-temperature total oxidation of propane:structural effects,kinetics,and spectroscopic investigation[J].Chinese Journal of Catalysis,2020,41(3):442-453.
[4]	赵磊,王筱喃,王新,等.石化VOC废气深度净化技术开发及工业应用[J].环境工程,2016,34(增刊1):569-571,579.
[5]	TOMITA A,MIKI T,TAI Y.Effect of water treatment and Ce doping of Pt/Al₂O₃ catalysts on Pt sintering and propane oxidation[J].Research on Chemical Intermediates,2021,47:2935-2950.
[6]	WU Q,YAN J,JIANG M,et al.Phosphate-assisted synthesis of ultrathin and thermally stable alumina nanosheets as robust Pd support for catalytic combustion of propane[J].Applied Catalysis B:Environment,2021,286:119949.
[7]	WANG Z,HUANG Z,BROSNAHAN J T,et al.Ru/CeO₂ catalyst with optimized CeO₂ support morphology and surface facets for propane combustion[J].Environmental Science & Technology,2019,53(9):5349-5358.
[8]	李娟娟,张梦,蔡松财,等.光热催化氧化VOCs的研究进展[J].环境工程,2020,38(1):13-20.
[9]	LI P,NAN C Y,WEI Z,et al.Mn₃O₄ nanocrystals:facile synthesis,controlled assembly,and application[J].Chemistry of Materials,2020,22(14):4232-4236.
[10]	赵海楠,王健,徐文青,等.锰氧化物催化氧化挥发性有机物(VOCs)研究进展[J].环境工程,2017,37(10):157-167.
[11]	CAI L N,GUO Y,LU A H,et al.The choice of precipitant and precursor in the co-precipitation synthesis of copper manganese oxide for maximizing carbon monoxide oxidation[J].Journal of Molecular Catalysis A:Chemical,2012,360:35-41.
[12]	WANG J J,TIAN P,LI K X,et al.The excellent performance of nest-like oxygen-deficient Cu_1.5Mn_1.5O₄ applied in activated carbon air-cathode microbial fuel cell[J].Bioresource Technology,2016,222:107-113.
[13]	ZHAO H,ZHOU X X,PAN L Y,et al.Facile synthesis of spinel Cu_1.5Mn_1.5O₄ microspheres with high activity for the catalytic combustion of diesel soot[J].RSC Advances,2017,7:20451-20459.
[14]	LIU T K,YAO Y Y,WEI L Q,et al.Preparation and evaluation of copper-manganese oxide as a high-efficiency catalyst for CO oxidation and NO reduction by CO[J].The Journal of Physical Chemistry C,2017,121(23):12757-12770.
[15]	郑海龙,廖菽欢,余林.介孔Cu-Mn复合氧化物催化氧化苯甲醇合成苯甲醛的研究[J].广东工业大学学报,2017,34(2):28-33.
[16]	杨德宇,郝庆兰,赵晨晨,等.Cu_xMn_1-_xCe_0.75Zr_0.25O_y催化降解甲苯的性能[J].环境工程,2021,39(1):96-100.
[17]	梁彦正,王学涛,罗绍峰,等.改性Cu-Mn/SAPO-34催化剂在SCR脱硝反应中的特性研究[J].燃料化学学报,2020,48(6):728-734.
[18]	元宁,杜冰洁,贾晓霞,等.双金属金属有机骨架材料的制备及性能研究进展[J].应用化学,2018,35(5):18-28.
[19]	牛照栋,周玲玲,关清卿,等.双金属类MOF材料的制备及应用[J].化工新型材料,2019,47(8):5-8.
[20]	PENG B,FENG C,LIU S,et al.Synthesis of CuO catalyst derived from HKUST-1 temple for the low-temperature NH₃-SCR process[J].Catalysis Today,2018,314:122-128.
[21]	LI M,WENG D,WU X D,et al.Importance of re-oxidation of palladium by interaction with lanthana for propane combustion over Pd/Al₂O₃ catalyst[J].Catalysis Today,2013,201:19-24.
[22]	CAO Y D,RAN R,CHEN Y S,et al.Nanostructured platinum in ordered mesoporous silica as novel efficient catalyst for propane total oxidation[J].RSC Advances,2016,6:30170-30175.
[23]	孙若琳,张斯然,安康,等.CuO修饰的Cu_1.5Mn_1.5O₄尖晶石型复合氧化物对CO氧化的协同催化[J].燃料化学学报,2021,49(6):799-808.
[24]	樊灏,沈振兴,逯佳琪,等.常温除甲醛催化剂Mn₁Ce_x/HZSM-5的活性位点与性能分析[J].环境工程,2021,39(6):99-105.
[25]	JEON W,CHOI I H,PARK J Y,et al.Alkaline wet oxidation of lignin over Cu-Mn mixed oxide catalysts for production of vanillin[J].Catalysis Today,2020,352:95-103.
[26]	胡总,黄振鹏,王征,等.Mn-Ce催化剂的制备及其在丙烷催化燃烧中的应用[J].中国稀土学报,2018,36(4):431-436.
[27]	ZHENG X H,CAI J M,CAO Y N,et al.Construction of cross-linked δ-MnO₂ with ultrathin structure for the oxidation of H₂S:structure-activity relationship and kinetics study[J].Applied Catalysis B:Environmental,2021,297:120402.