非贵金属催化剂催化氧化甲醛的研究进展

doi:10.16085/j.issn.1000-6613.2017-2547

摘要/Abstract

摘要： 室内装修装饰材料释放出的甲醛是一级致癌物质，严重危害人类的身体健康。催化氧化法在较为温和的条件下可以将甲醛转化为无毒的CO₂和H₂O，是一种非常有效的消除甲醛技术。其中该技术采用的非贵金属催化剂因资源丰富，价格低廉，目前研究的最为广泛。本文综述了近年来非贵金属催化剂的研究进展，主要介绍了单一金属氧化物和复合金属氧化物的研发情况；对这些催化剂的合成、结构及甲醛催化氧化性能进行了分析，并总结了一部分甲醛催化氧化的反应机理。另外还对非贵金属催化剂未来的研究发展方向进行了展望：通过各种制备方法调控金属氧化物的结构、形貌、比表面积，进而暴露大面积活性面和丰富优化活性位来提高催化性能；同时借助一些先进的表征技术和理论计算方法探索非贵金属催化剂结构和催化性能之间的关系，深入探讨甲醛催化氧化反应机理等基础问题。

关键词: 甲醛, 催化, 氧化, 非贵金属催化剂, 活性

Abstract: Formaldehyde (HCHO), mainly originated from furnishing and building materials, can endanger human health and has been classified as a human carcinogen. Catalytic oxidation of HCHO is considered as an ideal way to remove HCHO since it can completely convert HCHO into CO₂ and H₂O at relatively mild operating conditions. Among numerous catalyst systems, non-noble metal catalytic materials have been widely studied due to the cheap and plentiful sources. In this paper, the recent progresses of the non-noble metal catalysts in the catalytic oxidation of HCHO have been summarized. These non-noble metal catalysts mainly consist of single metal oxides and composite metal oxides. Their synthesis, structure and catalytic performance for the oxidation of HCHO reaction are analyzed. Besides, the reaction mechanisms have also been summarized. The opportunities for future research are:① to further enhance the catalytic activity by controlling the structure, morphology, and specific surface area of the non-noble metal catalysts, so as to expose larger fractions of the reactive facets, and to enrich and tune the active sites; ② to deeply reveal the structure-activity relationships of the catalysts and the reaction mechanisms by combining some advanced characterization techniques and theoretical computations.

Key words: formaldehyde, catalysis, oxidation, non-noble metal catalysts, reactivity

中图分类号:

TQ426

崔维怡, 惠继星, 谭乃迪. 非贵金属催化剂催化氧化甲醛的研究进展[J]. 化工进展, 2018, 37(11): 4286-4293.

CUI Weiyi, HUI Jixing, TAN Naidi. Research progress on catalytic oxidation of formaldehyde over non-noble metal catalysts[J]. Chemical Industry and Engineering Progress, 2018, 37(11): 4286-4293.

参考文献

[1] TUNGA S, SIBEL M, RAINER M.Formaldehyde in the indoor environment[J]. Chemical Reviews, 2010, 110:2536-2572.
[2] 何运兵, 纪红兵, 王乐夫.室内甲醛催化氧化脱除的研究进展[J]. 化工进展, 2007, 26(8):1104-1109. HE Y B, JI H B, WANG L F. Development of the removal of indoor formaldehyde with catalytic oxidation[J].Chemical Industry and Engineering Progress, 200, 26(8):1104-1109.
[3] TANG X J, BAI Y, DUONG A, et al.Formaldehyde in China:production, consumption, exposure levels, and health effects[J]. Environment International, 2009, 35:1210-1224.
[4] MARSH G M, YOUK A O.Reevaluation of mortality risks from nasopharyngeal cancer in the formaldehyde cohort study of the national cancer institute[J]. Regul Toxicol Pharmacol, 2005, 42:275-283.
[5] GILBERT N L, GUAY M, GAUVINB D, et al. Air change rate and concentration of formaldehyde in residential indoor air[J]. Atmospheric Environment, 2008, 42(10):2424-2428.
[6] ZHENG Y X, DING H, LUO H N, et al.Adsorption properties of formaldehyde by organic modified zeolite[J]. Advanced Materials Research, 2012, 581:277-282.
[7] LU N, PEI J J, ZHAO Y X, et al.Performance of a biological degradation method for indoor formaldehyde removal[J].Building and Environment, 2012, 57:253-258.
[8] 董冰岩, 施志勇, 何俊文, 等.脉冲放电等离子体协同Mn/TiO₂-分子筛、Fe/TiO₂-分子筛、Cu/TiO₂-分子筛催化剂降解甲醛[J]. 化工进展, 2015, 35(9):3337-3344. DONG B Y, SHI Z Y, HE J W, et al.Research of pulse discharge plasma combined with Mn/TiO₂-molecular、Fe/TiO₂-molecular、Cu/TiO₂-molecular sieve catalysts decomposition of formaldehyde[J]. Chemical Industry and Engineering Progress, 2015, 35(9):3337-3344.
[9] DARIA K, MOHAMAD S, JAVIERA C S, et al.Adsorption and photocatalytic oxidation of formaldehyde on a clay-TiO₂ composite[J]. Journal of Hazardous Materials, 2012, 211/212:233-239.
[10] JHON Q T, SEBASTIEN Y, BELLAT J P, et al.Formaldehyde:catalytic oxidation as a promising soft way of elimination[J]. ChemSusChem, 2013, 6:578-592.
[11] NIE L H, YU J G, JARONIEC M, et al.Room-temperature catalytic oxidation of formaldehyde on catalysts[J]. Catalysis Science & Technology, 2016, 6:3649-3669.
[12] BAI B Y, QIAO Q, LI J H, et al.Progress in research on catalysts for catalytic oxidation of formaldehyde[J].Chinese Journal of Catalysis, 2016, 37:102-122.
[13] SHEN Y, YANG X, WANG Y, et al.The states of gold species in CeO₂ supported gold catalyst for formaldehyde oxidation[J]. Applied Catalysis B:Environmental, 2008, 79(2):142-148.
[14] 崔维怡, 惠继星, 谭乃迪.负载型铂催化剂催化氧化甲醛的研究进展[J]. 化工进展, 2017, 36(10):3711-3719. CUI W Y, HUI J X, TAN N D.Research progress on catalytic oxidation of formaldehyde over supported platinum catalysts[J]. Chemical Industry and Engineering Progress, 2017, 36(10):3711-3719.
[15] ZHANG C B, LI Y B, WANG Y F, et al.Sodium-promoted Pd/TiO₂ for catalytic oxidation of formaldehyde at ambient temperature[J]. Environmental Science &Technology, 2014, 48:5816-5822.
[16] BAI B Y, QIAO Q, ARANDIYAN H, et al.Three-dimensional ordered mesoporous MnO₂-supported Ag nanoparticles for catalytic removal of Formaldehyde[J]. Environmental Science & Technology, 2016, 50:2635-2640.
[17] BAI B Y, ARANDIYAN H, LI J H.Comparison of the performance for oxidation of formaldehyde on nano-Co₃O₄, 2D-Co₃O₄, and 3D-Co₃O₄ catalysts[J].Applied Catalysis B:Environmental, 2013, 142/143:677-683.
[18] XIA Y S, DAI H X, ZHANG L, et al.Ultrasound-assisted nanocasting fabrication and excellent catalytic performance of three-dimensionally ordered mesoporous chromia for the combustion of formaldehyde, acetone, and methanol[J].Applied Catalysis B:Environmental, 2010, 100:229-237.
[19] 李玮, 黄丽丽, 翟友存, 等.新型Cu-Mn/TiO₂和Cu-Mn/γ-Al₂O₃甲醛催化氧化催化剂的研制及活性[J]. 化工进展, 2015, 34(1):127-132. LI W, HUANG L L, ZHAI Y C, et al.Catalytic oxidation of formaldehyde over Cu-Mn catalysts supported on TiO₂ and γ-Al₂O₃ dioxide[J].Chemical Industry and Engineering Progress, 2015, 34(1):127-132.
[20] MA L, WANG D S, LI J H, et al.Ag/CeO₂ nanospheres:efficient catalysts for formaldehyde oxidation[J].Applied Catalysis B:Environmental, 2014, 148/149:36-43.
[21] MENEZES P W, INDRA A, LITTLEWOOD P, et al.Nanostructured manganese oxides as highly active water oxidation catalysts:a boost from manganese precursor chemistry[J].ChemSusChem, 2014, 7:2202-2211.
[22] SEKINE Y, NISHIMURA A.Removal of formaldehyde from indoor air by passive type air-cleaning materials[J]. Atmospheric Environment, 2001, 35(11):2001-2007.
[23] TANG X F, HUANG X M, SHAO J J, et al.Synthesis and catalytic performance of manganese oxide octahedral molecular sieve nanorods for formaldehyde oxidation at low temperature[J]. Chinese Journal of Catalysis, 2006, 2:97-99.
[24] TIAN H, HE J, ZHANG X, et al.Facile synthesis of porous manganese oxide K-OMS-2 materials and their catalytic activity for formaldehyde oxidation[J]. Microporous and Mesoporous Materials, 2011, 138(1-3):118-122.
[25] CHEN T, DOU H Y, LI X L, et al. Tunnel structure effect of manganese oxides in complete oxidation of formaldehyde[J]. Microporous and Mesoporous Materials, 2009, 122:270-274.
[26] ZHANG J H, LI Y B, WANG L, et al.Catalytic oxidation of formaldehyde over manganese oxides with different crystal structures[J].Catalysis Science Technology, 2015, 5:2305-2313.
[27] ZHOU L, ZHANG J, HE J H, et al.Control over the morphology and structure of manganese oxide by tuning reaction conditions and catalytic performance for formaldehyde oxidation[J].Materials Research Bulletin, 2011, 46:1714-1722.
[28] WANG M, ZHANG L X, HUANG W M, et al.The catalytic oxidation removal of low-concentration HCHO at high space velocity by partially crystallized mesoporous MnO_x[J]. Chemical Engineering Journal, 2017, 320:667-676.
[29] BAI B Y, QIAO Q, LI J Y, et al.Synthesis of three-dimensional ordered mesoporous MnO₂ and its catalytic performance in formaldehyde oxidation[J].Chinese Journal of Catalysis, 2016, 37:27-31.
[30] WANG J L, LI D D, LI P L, et al.Layered manganese oxides for formaldehyde-oxidation at room temperature:the effect of interlayer cations[J].RSC Advances, 2015, 5:100434-100442.
[31] ZHAO D Z, SHI C, LI X S, et al.Enhanced effect of water vapor on complete oxidation of formaldehyde in air with ozone over MnO_x catalysts at room temperature[J]. Journal of Hazardous Materials, 2012, 239/240:362-369.
[32] TORRES J Q, GIRAUDON J M, LAMONIER J F.Formaldehyde total oxidation over mesoporous MnO_x catalysts[J]. Catalysis Today, 2011, 176:277-280.
[33] XIE X W, LI Y, LIU Z Q, et al. Low-temperature oxidation of CO catalysed by Co₃O₄ nanorods[J]. Nature, 2009, 458:746-749.
[34] WANG Z, WANG W Z, ZHANG L, et al.Surface oxygen vacancies on Co₃O₄ mediated catalytic formaldehyde oxidation at room temperature[J]. Catalysis Science & Technology, 2016, 6:3845-3853.
[35] FAN Z Y, ZHANG Z X, FANG W J, et al.Low-temperature catalytic oxidation of formaldehyde over Co₃O₄ catalysts prepared using various precipitants[J]. Chinese Journal of Catalysis, 2016, 37:947-954.
[36] ZENG L, SONG W L, LI M H, et al.Catalytic oxidation of formaldehyde on surface of H-TiO₂/H-C-TiO₂ without light illumination at room temperature[J]. Applied Catalysis B:Environmental, 2014, 147:490-498.
[37] ZOU Z Q, MENG M, ZHA Y Q.Surfactant-assisted synthesis, characterizations, and catalytic oxidation mechanisms of the mesoporous MnO_x-CeO₂ and Pd/MnO_x-CeO₂ catalysts used for CO and C₃H₈ oxidation[J]. The Journal of Physical Chemistry C, 2010, 114:468-477.
[38] TANG X F, LI Y G, HUANG X M, et al.MnO_x-CeO₂ mixed oxide catalysts for complete oxidation of formaldehyde:effect of preparation method and calcination temperature[J]. Applied Catalysis B:Environmental, 2006, 62:265-273.
[39] QUIRON J, GIRAUDON J M, GERVASINI A, et al.Total oxidation of formaldehyde over MnO_x-CeO₂ catalysts:the effect of acid treatment[J]. ACS Catalysis, 2015, 5:2260-2269.
[40] AGUILERA D A, PEREZ A, MOLINA R, et al.Cu-Mn and Co-Mn catalysts synthesized from hydrotalcites and their use in the oxidation of VOCs[J]. Applied Catalysis B:Environmental, 2011, 104:144-150.
[41] SHI C, WANG Y, ZHU A M, et al.Mn_xCo_3-x O₄ solid solution as high-efficient catalysts for low-temperature oxidation of formaldehyde[J]. Catalysis Communications, 2012, 28:18-22.
[42] WANG Y, ZHU A M, CHEN B B, et al.Three-dimensional ordered mesoporous Co-Mn oxide:a highly active catalyst for "storage-oxidation" cycling for the removal of formaldehyde[J]. Catalysis Communications, 2013, 36:52-57.
[43] LIU P, HE H P, WEI G L, et al.Effect of Mn substitution on the promoted formaldehyde oxidation over spinel ferrite:catalyst characterization, performance and reaction mechanism[J]. Applied Catalysis B:Environmental, 2016, 182:476-484.
[44] LIANG X L, LIU P, HE H P, et al.The variation of cationic microstructure in Mn-doped spinel ferrite during calcination and its effect on formaldehyde catalytic oxidation[J].Journal of Hazardous Materials, 2016, 306:305-312.
[45] HUANG Y C, FAN W J, LONG B, et al.Alkali-modified non-precious metal 3D-NiCo₂O₄ nanosheets for efficient formaldehyde oxidation at low temperature[J]. Journal of Materials Chemistry A, 2016, 4:3648-3654.
[46] HUANG Y C, LI H B, BALOGUN M S, et al.Three-dimensional TiO₂/CeO₂ nanowire composite for efficient formaldehyde oxidation at low temperature[J].RSC Advances, 2015, 5:7729-7733.
[47] HUANG F L, CHEN C C, WANG F, et al.Effect of calcination temperature on the catalytic oxidation of formaldehyde over Co₃O₄- CeO₂ catalysts[J]. Catalysis Surveys from Asia, 2017, 21:143-149.
[48] XU J, WHITE T, LI P, et al.Hydroxyapatite foam as a catalyst for formaldehyde combustion at room temperature[J]. Journal of the American Chemical Society, 2010, 132:13172-13173.
[49] WANG J L, ZHANG P Y, LI J G, et al.Room-temperature oxidation of formaldehyde by layered manganese oxide:effect of water[J]. Environmental Science &Technology, 2015, 49:12372-12379.