钴锰整体式催化剂的电沉积法制备及NO催化氧化性能

doi:10.16085/j.issn.1000-6613.2019-0090

摘要/Abstract

摘要：

整体式催化剂性能高效、应用广泛，而制备方法是影响其性能的关键因素，因此探究简单高效的制备方法对整体式催化剂的工业应用至关重要。本研究以碳纤维布为载体，采用电沉积方法制备了一系列钴锰整体式催化剂，在固定床反应装置上考察了其催化氧化NO性能，并借助拉曼光谱仪、X射线衍射仪和扫描电镜等分析技术对催化剂进行表征。结果表明，采用电沉积法制备的钴锰二元催化剂比相同方法制备的氧化钴或氧化锰一元催化剂的粒径小，且钴锰比例对催化剂粒径影响很大，最小粒径为3～4nm。不同摩尔比例的钴锰二元催化剂焙烧之后物相差别较大，Mn/Co较高的催化剂的主要组成为Mn₃O₄，Mn/Co较低则趋向Co₃O₄，其中Mn/Co=2时，催化剂为(CoMn)(CoMn)₂O₄。电沉积法制备的钴锰整体式催化剂催化氧化NO的性能要远优于相同方法制备的氧化锰催化剂,在50℃下转化率均接近100%。

关键词: 催化剂, 电化学, 复合材料, 整体器件, 纳米材料

Abstract:

Monolithic catalysts are widely applied in various fields, and exploration on preparation methods for monolithic catalysts is critical for industrial applications. A series of Mn-Co monolithic catalysts of Mn/Co with different molar ratios immobilized on carbon fiber cloth substrate were prepared by electrodeposition method, and their NO oxidation activities were evaluated. Raman, XRD, SEM and other techniques were used to characterize the catalysts. The results showed that the Mn-Co binary catalyst prepared by electrodeposition method had a smaller particle size than cobalt oxide or manganese oxide unary catalyst by same method, and the minimum particle size was 3—4nm. Different Mn/Co molar ratios affected the catalyst particle size and phases a lot. The main substance after calcination of the catalyst with the highest manganese content was Mn₃O₄. With the cobalt content increasing, the main phase changed to Co₃O₄, but when Mn/Co=2, the phase of the catalyst was (CoMn)(CoMn)₂O₄. Co/Mn-based catalysts prepared by electrodeposition had much better NO catalytic activity than manganese oxide catalyst prepared by same method, its conversion was closed to 100% at 50℃.

Key words: catalyst, electrochemistry, composites, monolith, nanomaterials

中图分类号:

X131.1

刘喆,王泽轩,肖蓓,蔡婷,袁静,赵昆峰,何丹农. 钴锰整体式催化剂的电沉积法制备及NO催化氧化性能[J]. 化工进展, 2019, 38(10): 4588-4594.

Zhe LIU,Zexuan WANG,Bei XIAO,Ting CAI,Jing YUAN,Kunfeng ZHAO,Dannong HE. Electrodeposition preparation and NO catalytic capacity of Co/Mn-based monolithic catalysts[J]. Chemical Industry and Engineering Progress, 2019, 38(10): 4588-4594.

图/表 8

图1 不同钴锰元素比整体式催化剂的TG图

图2 不同钴锰元素比的整体式催化剂及碳纤维布焙烧前后的FTIR对比图

图3 不同钴锰元素比与氧化钴、氧化锰整体式催化剂及碳纤维布焙烧前后的Raman图

图4 焙烧后不同钴锰元素比的二元整体式催化剂XRD图谱

图5 不同钴锰元素比的二元催化剂SEM图

图6 MC 2焙烧前后的SEM形貌对比图

图7 焙烧后不同钴锰元素比的二元材料TEM图

图8 焙烧后不同催化剂活性对比图

参考文献 33

1	LIU H , YANG D , GAO R , et al . A novel Na₂WO₄-Mn/SiC monolithic foam catalyst with improved thermal properties for the oxidative coupling of methane[J]. Catalysis Communications, 2008, 9(6): 1302-1306.
2	CHAI R , LI Y , ZHANG Q , et al . Free-standing NiO-MgO nanosheets in-situ controllably composited on Ni-foam as monolithic catalyst for catalytic oxy-methane reforming[J]. Materials Letters, 2016, 171: 248-251.
3	CHEN S , WEI Z , QI X Q , et al . Nanostructured polyaniline-decorated Pt/C@PANI core-shell catalyst with enhanced durability and activity[J]. Journal of the American Chemical Society, 2012, 134(32): 13252-13255.
4	AKBAR S , ELLIOTT J M , RITTMAN M , et al . Facile production of ordered 3D platinum nanowire networks with "single diamond" bicontinuous cubic morphology[J]. Advanced Materials, 2013, 25(8): 1160-1164.
5	NIE Y , LI L , WEI Z . Recent advancements in Pt and Pt-free catalysts for oxygen reduction reaction[J]. Chemical Society Reviews, 2015, 44(8): 2168-2201.
6	ZHANG N , GAN S , WU T , et al . Growth control of MoS₂ nanosheets on carbon cloth for maximum active edges exposed: an excellent hydrogen evolution 3D cathode[J]. ACS Applied Materials & Interfaces, 2015, 7(22): 12193-12202.
7	XU Y F , CHEN Y , XU G L , et al . RuO₂ nanoparticles supported on MnO₂ nanorods as high efficient bifunctional electrocatalyst of lithium-oxygen battery[J]. Nano Energy, 2016, 28: 63-70.
8	JING G J , ZHANG X J , ZHANG A A , et al . CeO₂-CuO/Cu₂O/Cu monolithic catalysts with three-kind morphologies Cu₂O layers for preferential CO oxidation[J]. Applied Surface Science, 2018, 434: 445-451.
9	LI W , YE H Q , LIU G G , et al . The role of graphene coating on cordierite-supported Pd monolithic catalysts for low-temperature combustion of toluene[J]. Chinese Journal of Catalysis, 2018, 39(5): 946-954.
10	LI Y S , XU H D , FENG X , et al . The effective promotion of trace amount of Cu on Ce/WO₃-ZrO₂-TiO₂ monolithic catalyst for the low-temperature NH₃-SCR of NO _x [J]. Canadian Journal of Chemical Engineering, 2018, 96(5): 1168-1175.
11	PORCAR R , NUEVO D , GARCIA-VERDUGO E , et al . New porous monolithic membranes based on supported ionic liquid-like phases for oil/water separation and homogenous catalyst immobilisation[J]. Chemical Communications, 2018, 54(19): 2385-2388.
12	RASMUSSEN S B , PORTELA R , BAZIN P , et al . Transient operando study on the NH₃/NH₄ ⁺ interplay in V-SCR monolithic catalysts[J]. Applied Catalysis B: Environmental, 2018, 224: 109-115.
13	ZHANG K , YU F , ZHU M Y , et al . Enhanced low temperature NO reduction performance via MnO _x -Fe₂O₃/vermiculite monolithic honeycomb catalysts[J]. Catalysts, 2018, 8(3): 100.
14	ZHOU H , GE M Y , WU S G , et al . Iron based monolithic catalysts supported on Al₂O₃, SiO₂, and TiO₂: a comparison for NO reduction with propane[J]. Fuel, 2018, 220: 330-338.
15	ZHOU M M , SHI Y F , MA K , et al . Nanoarray Cu/SiO₂ catalysts embedded in monolithic channels for the stable and efficient hydrogenation of CO₂-derived ethylene carbonate[J]. Industrial & Engineering Chemistry Research, 2018, 57(6): 1924-1934.
16	GONG M , DAI H . A mini review of NiFe-based materials as highly active oxygen evolution reaction electrocatalysts[J]. Nano Research, 2014, 8(1): 23-39.
17	FENG J X , DING L X , YE S H , et al . Co(OH)₂@PANI hybrid nanosheets with 3D networks as high-performance electrocatalysts for hydrogen evolution reaction[J]. Advanced Materials, 2015, 27(44): 7051-7057.
18	BADALYAN A , STAHL S S . Cooperative electrocatalytic alcohol oxidation with electron-proton-transfer mediators[J]. Nature, 2016, 535(7612): 406-410.
19	VALKOVA T , KRASTEV I , Influence of glycine on the electrochemical deposition of Sn-Co alloy from gluconate electrolyte [J]. Bulgarian Chemical Communications, 2016, 48: 78-84.
20	ZHANG X X , ZHANG H H , QIAN M F , et al . Enhanced magnetocaloric effect in Ni-Mn-Sn-Co alloys with two successive magnetostructural transformations[J]. Scientific Reports, 2018, 8: 8235.
21	LIU H , MA X , RAO Y , et al . Heteromorphic NiCo₂S₄/Ni₃S₂/Ni foam as a self-standing electrode for hydrogen evolution reaction in alkaline solution[J]. ACS Applied Materials & Interfaces, 2018, 10(13): 10890-10897.
22	YUAN G , NIU X P , CHEN Z C , et al . Self-supported hierarchical shell@core Ni₃S₂@Ni foam composite electrocatalyst with high efficiency and long-term stability for methanol oxidation[J]. ChemElectroChem, 2018, 5(17): 2376-2382.
23	CAO M , XUE Z , NIU J J , et al . Facile electrodeposition of Ni-Cu-P dendrite nanotube films with enhanced hydrogen evolution reaction activity and durability[J]. ACS Applied Materials & Interfaces, 2018, 10(41): 35224-35233.
24	CAO X , HONG Y , ZHANG N , et al . Phase exploration and identification of multinary transition-metal selenides as high-efficiency oxygen evolution electrocatalysts through combinatorial electrodeposition[J]. ACS Catalysis, 2018, 8(9): 8273-8289.
25	XIAO B , ZHAO K F , ZHANG L , et al . A green and facile synthesis of Co₃O₄ monolithic catalyst with enhanced total oxidation of propane performance[J]. Catalysis Communications, 2018, 116: 1-4.
26	廖永进, 张亚平, 朱一闻, 等 . WO₃掺杂对V₂O₅/TiO₂-SnO₂催化剂NH₃选择性催化还原NO _x 的影响[J]. 化工进展, 2017，36(3): 951-956.
	LIAO Y J , ZHANG Y P , ZHU Y W , et al . Influence of WO₃ doping on properties of V₂O₅/TiO₂-SnO₂ catalysts for selective catalytic reduction of NO _x by NH₃ [J]. Chemical Industry and Engineering Progress, 2017，36(3): 951-956.
27	任瑞鹏, 陈虎, 陈健, 等 . 应用催化氧化催化剂脱除烟气中NO的研究进展[J]. 化工进展, 2014， 33(6): 1453-1458.
	REN R P , CHEN H , CHEN J , et al . Study on catalytic oxidations catalysts in removal of NO from flue gas[J]. Chemical Industry and Engineering Progress, 2014, 33(6): 1453-1458.
28	SHU Z , HUANG W M , HUA Z L , et al . Template-free synthesis of mesoporous X-Mn (X = Co, Ni, Zn) bimetal oxides and catalytic application in the room temperature removal of low-concentration NO[J]. Journal of Materials Chemistry A, 2013, 1(35): 10218-10227.
29	SHUANG L , ZHANG M , HUANG Y , et al . A novel chromic oxide catalyst for NO oxidation at ambient temperature[J]. RSC Advances, 2014, 4(55): 29180-29186.
30	SHU Z , CHEN Y , HUANG W , et al . Room-temperature catalytic removal of low-concentration NO over mesoporous Fe-Mn binary oxide synthesized using a template-free approach[J]. Applied Catalysis B: Environmental, 2013, 140/141(8): 42-50.
31	GUO Z , LIANG Q H , YANG Z , et al . Modifying porous carbon nanofibers with MnO _x -CeO₂-Al₂O₃ mixed oxides for NO catalytic oxidation at room temperature[J]. Catalysis Science & Technology, 2016, 6(2): 422-425.
32	GUO Z , HUANG Z H , WANG M , et al . Graphene/carbon composite nanofibers for NO oxidation at room temperature[J]. Catalysis Science & Technology, 2015, 5(2): 827-829.
33	IWAMOTO M , YODA Y , YAMAZOE N , et al . Study of metal oxide catalysts by temperature programmed desorption 4. oxygen adsorption on various metal oxides[J]. The Journal of Physical Chemistry, 82(24): 2564-2570.

[1]	张明焱, 刘燕, 张雪婷, 刘亚科, 李从举, 张秀玲. 非贵金属双功能催化剂在锌空气电池研究进展[J]. 化工进展, 2023, 42(S1): 276-286.
[2]	时永兴, 林刚, 孙晓航, 蒋韦庚, 乔大伟, 颜彬航. 二氧化碳加氢制甲醇过程中铜基催化剂活性位点研究进展[J]. 化工进展, 2023, 42(S1): 287-298.
[3]	谢璐垚, 陈崧哲, 王来军, 张平. 用于SO₂去极化电解制氢的铂基催化剂[J]. 化工进展, 2023, 42(S1): 299-309.
[4]	杨霞珍, 彭伊凡, 刘化章, 霍超. 熔铁催化剂活性相的调控及其费托反应性能[J]. 化工进展, 2023, 42(S1): 310-318.
[5]	胡喜, 王明珊, 李恩智, 黄思鸣, 陈俊臣, 郭秉淑, 于博, 马志远, 李星. 二硫化钨复合材料制备与储钠性能研究进展[J]. 化工进展, 2023, 42(S1): 344-355.
[6]	张杰, 白忠波, 冯宝鑫, 彭肖林, 任伟伟, 张菁丽, 刘二勇. PEG及其复合添加剂对电解铜箔后处理的影响[J]. 化工进展, 2023, 42(S1): 374-381.
[7]	王乐乐, 杨万荣, 姚燕, 刘涛, 何川, 刘逍, 苏胜, 孔凡海, 朱仓海, 向军. SCR脱硝催化剂掺废特性及性能影响[J]. 化工进展, 2023, 42(S1): 489-497.
[8]	邓丽萍, 时好雨, 刘霄龙, 陈瑶姬, 严晶颖. 非贵金属改性钒钛基催化剂NH₃-SCR脱硝协同控制VOCs[J]. 化工进展, 2023, 42(S1): 542-548.
[9]	程涛, 崔瑞利, 宋俊男, 张天琪, 张耘赫, 梁世杰, 朴实. 渣油加氢装置杂质沉积规律与压降升高机理分析[J]. 化工进展, 2023, 42(9): 4616-4627.
[10]	王鹏, 史会兵, 赵德明, 冯保林, 陈倩, 杨妲. 过渡金属催化氯代物的羰基化反应研究进展[J]. 化工进展, 2023, 42(9): 4649-4666.
[11]	张启, 赵红, 荣峻峰. 质子交换膜燃料电池中氧还原反应抗毒性电催化剂研究进展[J]. 化工进展, 2023, 42(9): 4677-4691.
[12]	王伟涛, 鲍婷玉, 姜旭禄, 何珍红, 王宽, 杨阳, 刘昭铁. 醛酮树脂基非金属催化剂催化氧气氧化苯制备苯酚[J]. 化工进展, 2023, 42(9): 4706-4715.
[13]	葛亚粉, 孙宇, 肖鹏, 刘琦, 刘波, 孙成蓥, 巩雁军. 分子筛去除VOCs的研究进展[J]. 化工进展, 2023, 42(9): 4716-4730.
[14]	林晓鹏, 肖友华, 管奕琛, 鲁晓东, 宗文杰, 傅深渊. 离子聚合物-金属复合材料（IPMC）柔性电极的研究进展[J]. 化工进展, 2023, 42(9): 4770-4782.
[15]	雷伟, 姜维佳, 王玉高, 和明豪, 申峻. N、S共掺杂煤基碳量子点的电化学氧化法制备及用于Fe³⁺检测[J]. 化工进展, 2023, 42(9): 4799-4807.