Page 54 - 《精细化工》2020年 第10期

·1984· 精细化工 FINE CHEMICALS 第 37 卷

5 结语与展望 Science & Technology, 2015, 5: 2649-2669.
[7] NIE L H, YU J G, JARONIEC M, et al. Room-temperature catalytic
oxidation of formaldehyde on catalysts[J]. Catalysis Science &
目前，应用于甲醛催化氧化的催化剂研究取得
Technology, 2016, 6: 3649-3669.
了较大的进展，获得了一大批高活性的催化剂，但 [8] BAI B Y, QIAO Q, LI J H, et al. Progress in research on catalysts for
是，在甲醛催化反应机理方面的研究还存在不足。 catalytic oxidation of formaldehyde[J]. Chinese Journal of Catalysis,
2016, 37(1): 102-122.
在催化反应过程中，甲醛需要在催化剂表面发 [9] GUO J H, LIN C X, JIANG C J, et al. Review on noble metal-based
生吸附、反应和转换等过程，因而，催化反应机理 catalysts for formaldehyde oxidation at room temperature[J]. Applied
Surface Science, 2019, 475: 237-255.
研究是一个比较复杂的过程。目前，借助 DRIFTS
[10] WANG X Y, RUI Z B, JI H B. DFT study of formaldehyde oxidation
技术通过监测特征红外波段的时间变化，可以识别 on silver cluster by active oxygen and hydroxyl groups: Mechanism
一些反应中间体，由此可以推断出可能的反应途径。 comparison and synergistic effect[J]．Catalysis Today, 2020, 347:
124-133.
但是，机理的反应细节并不很清楚，例如，甲醛催 [11] AN N H (安霓虹). Low-temperature catalytic oxidation of formaldehyde
化氧化反应过程中可能发生平行反应，因此，很难 and carbon monoxide over supported Pt catalysts[D]. Changchun:
Jilin University (吉林大学), 2012.
确定测定的中间物种参与了哪一个反应；在中间产
[12] CHEN D (陈丹). HCHO adsorption-desorption and catalytic oxidation
物 CO 发生氧化反应生成 CO 2 的过程中，并不确定 performance over Ag based catalysts[D]. Dalian: Dalian University
是气相氧还是吸附氧与 CO 进行反应；甲酸是如何 of Technology (大连理工大学), 2014.
[13] WANG J L (王金龙). Room temperature catalytic decomposition of
分解的等问题。因此，具体反应机理的阐述还需要 formaldehyde by birnessite-type manganese dioxide[D]. Beijing:
进一步探索研究。 Tsinghua University (清华大学), 2016.
综上所述，对于甲醛催化氧化反应机理，今后 [14] NIE L H, YU J G, LI X Y, et al. Enhanced performance of NaOH-
modified Pt/TiO 2 toward room temperature selective oxidation of
的探索方向有：（1）借助快速发展的电子表征技术， formaldehyde[J]. Environmental Science & Technology, 2013, 47:
实时表征催化剂在不同反应条件或时间尺度下的反 2777-2783.
[15] YAN Z X, XU Z H, YU J G, et al. Effect of microstructure and surface
应中间体，例如精心设计实时 DRIFTS 实验，在监
hydroxyls on the catalytic activity of Au/AlOOH for formaldehyde
测反应过程中读取可能瞬时存在的中间体信息； removal at room temperature[J]. Journal of Colloid and Interface
（2）目前的催化剂实验体系多集中在评价催化性 Science, 2017, 501: 164-174.
[16] HU P P, AMGHOUZ Z, HUANG Z W, et al. Surface-confined atomic
能，对反应动力学还缺乏深入研究，一些催化剂体 silver centers catalyzing formaldehyde oxidation[J]. Environmental
系借助 DFT 计算得到结果都是基于理想条件，因此， Science & Technology, 2015, 49: 2384-2390.
[17] LI Y B, ZHANG C B, MA J Z, et al. High temperature reduction
考虑将理论计算与实验数据相结合，更准确地阐明
dramatically promotes Pd/TiO 2 catalyst for ambient formaldehyde
甲醛催化反应机理；（3）失活和中毒是催化基础研 oxidation[J]. Applied Catalysis B: Environmental, 2017, 217: 560-569.
究的重点，在甲醛室温氧化过程中，催化剂会存在 [18] CUI W Y, YUAN X L, WU P, et al. Catalytic properties of γ-Al 2O 3
supported Pt-FeO x catalysts for complete oxidation of formaldehyde
失活或中毒，因此，需要深入探讨催化剂表面化学 at ambient temperature[J]. RSC Advances, 2015, 5: 104330-104336.
与其相应的催化性能之间的关系，进而探索反应机 [19] CUI W Y, XUE D, TAN N D, et al. Octahedral Fe 3O 4 microcrystals
supported Pt catalysts for removal of formaldehyde at ambient
理。只有弄清甲醛催化氧化反应机理，设计出新型
conditions[J]. Chinese Journal of Catalysis, 2018, 39: 1534-1542.
高效的催化剂，才能让催化氧化技术在实际的室内 [20] DENG J L, SONG W Y, CHEN L L, et al. The effect of oxygen
空气污染治理中得到更加广泛的应用。 vacancies and water on HCHO catalytic oxidation over Co 3O 4 catalyst:
A combination of density functional theory and microkinetic study[J].
参考文献： Chemical Engineering Journal, 2019, 355: 540-550.
[21] WANG Z, WANG W Z, ZHANG L, et al. Surface oxygen vacancies
[1] TUNAGN S, SIBEL M, RAINER M. Formaldehyde in the indoor on Co 3O 4 mediated catalytic formaldehyde oxidation at room
environment[J]. Chemical Reviews, 2010, 110(4): 2536-2572. temperature[J]. Catalysis Science & Technology, 2016, 6: 3845-3853.
[2] TANG X J, BAI Y, DUONG A, et al. Formaldehyde in China: [22] ZHANG C B, HE H. A comparative study of TiO 2 supported noble metal
Production, consumption, exposure levels, and health effects[J]. catalysts for the oxidation of formaldehyde at room temperature[J].
Environment International, 2009, 35(8): 1210-1224. Catalysis Today, 2007, 126: 345-350.
[3] ZHAI L, ZHAO J, XU B, et al. Influence of indoor formaldehyde [23] GOMES J R B, GOMES J A N F. A theoretical study of dioxymethylene,
pollution on respiratory system health in the urban area of Shenyang, proposed as intermediate in the oxidation of formaldehyde to formate
China[J]. African Health Sciences, 2013, 13 (1): 137-143. over copper[J]. Surface Science, 2000, 446(3): 283-293.
[4] JIANG C J, LI D D, ZHANG P Y, et al. Formaldehyde and volatile [24] CHEN H Y, RUI Z B, JI H B. Monolith-like TiO 2 nanotube array
organic compound (VOC) emissions from particleboard: Identification supported Pt catalyst for HCHO removal under mild conditions[J].
of odorous compounds and effects of heat treatment[J]. Building and Industrial & Engineering Chemistry Research, 2014, 53: 7629-7636.
Environment, 2017, 117: 118-126. [25] CHEN H Y, RUI Z B, WANG X Y, et al. Multifunctional Pt/ZSM-5
[5] JHON Q T, SEBASTIEN Y, BELLAT J P, et al. Formaldehyde: catalyst for complete oxidation of gaseous formaldehyde at ambient
Catalytic oxidation as a promising soft way of elimination[J]. temperature[J]. Catalysis Today, 2015, 258: 56-63.
ChemSusChem, 2013, 6(4): 578-592. [26] LIU B T, HSIEH C H, WANG W H, et al. Enhanced catalytic oxidation
[6] HUANG H B, XU Y, FENG Q Y, et al. Low temperature catalytic of formaldehyde over dual-site supported catalysts at ambient
oxidation of volatile organic compounds: A review[J]. Catalysis temperature[J]. Chemical Engineering Journal, 2013, 232: 434-441.