临泽红色低品位凹凸棒石黏土负载δ-MnO<sub>2</sub>室温降解甲醛

洪晓梅; 陈天虎; 王灿; 邹雪华; 韩正严

doi:10.13801/j.cnki.fhclxb.20210609.001

临泽红色低品位凹凸棒石黏土负载δ-MnO₂室温降解甲醛

doi: 10.13801/j.cnki.fhclxb.20210609.001

合肥工业大学　资源与环境工程学院　纳米矿物与污染控制安徽省普通高校重点实验室，合肥 230009

基金项目: 国家自然科学基金(41872040；41772038)；临泽县凹凸棒石产业发展开放课题(LZKFKT-1902)

详细信息

通讯作者:
陈天虎，博士，教授，博士生导师，研究方向为纳米矿物的环境应用　E-mail：chentianhu@hfut.edu.cn

中图分类号: TB33
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出版历程
- 收稿日期: 2021-04-20
- 修回日期: 2021-06-01
- 录用日期: 2021-06-02
- 网络出版日期: 2021-06-09
- 刊出日期: 2022-04-01

δ-MnO₂ supported on low-grade Palygorskite clay from Linze as a catalyst for formaldehyde catalytic oxidation at room temperature

Key Laboratory of Nano-minerals and Pollution Control of Anhui Higher Education Institutes, School of Resources & Environmental Engineering, Hefei University of Technology, Hefei 230009, China

摘要

摘要: 针对临泽地区低品位凹凸棒石黏土利用率低的问题，用预富集处理的临泽红色低品位凹凸棒石黏土(PPCI)为载体，利用高锰酸钾和草酸铵为反应前驱体，通过氧化还原法制备MnO_x/PPCI复合催化剂，并用于常温下降解室内空气中甲醛效果评价。结果表明，Mn负载量为33.6wt%的复合催化剂具有优异性能，动态实验中，当进气甲醛浓度为1.22 mg/m³时，去除率在720 min内保持99%以上，而未负载的δ-MnO₂在相同条件下去除甲醛的效率仅为87%；静态实验中对初始浓度为146.6 mg/m³的甲醛气体去除率高达95%以上，PPCI负载δ-MnO₂可以显著提高锰基催化剂室温降解甲醛效果。δ-MnO₂/PPCI复合催化剂降解甲醛反应遵循二级动力学。由于δ-MnO₂在凹凸棒石黏土矿物表面高度分散，有更大的比表面积(73.2 m²/g)，可以暴露出更多Mn³⁺/Mn⁴⁺活性电对，从而提高了复合催化剂的氧化还原能力和电化学活性，并最终促进甲醛的降解。通过原位红外光谱(In situ-DRFTS)研究了甲醛在复合催化剂表面中间产物的生成和转化过程，结果表明甲醛首先被表面羟基转化为亚甲基二氧(DOM)，进而被表面活性氧氧化为甲酸盐物种(HCOO^-)，最终被氧化为CO₂和H₂O，并且催化反应消耗表面羟基可通过凹凸棒石表面吸附水与表面活性氧反应再生。本研究通过开发低品位凹凸棒石黏土，提高资源利用率，并为开发高效复合室内空气净化材料提供新思路。
- 低品位凹凸棒石 /
- 锰氧化物 /
- 甲醛 /
- 氧化降解 /
- 环境温度
Abstract: Aiming at the low utilization rate of low-grade palygorskite in Linze area, MnO_x/purifing palygorskite clay rich iron (PPCI) hybrid catalysts were prepared by the redox reaction method between KMnO₄ and (NH₄)₂C₂O₄ via using low-grade PPCI from Linze as the support. The δ-MnO₂/PPCI catalyst with Mn loading of 33.6wt% has excellent performance for formaldehyde oxidation at room temperature, which maintains more than effective 99% formaldehyde removal rate within 720 minutes. In contrast, the effective formaldehyde removal rate of the unloaded δ-MnO₂ sample is only 87% after 720 min. Also, the removal rate of formaldehyde with initial concentration of 146.6 mg/m³is more than 95% in 1h. The above results reveal that the introduction of palygorskite clay as the support greatly improves the efficiency of the MnO_x/PPCI hybrid catalysts at room temperature. The formaldehyde oxidation kinetics results follow the second-order kinetics. Manganese oxide was highly distributed on the surface of palygorskite, resulting in a larger specific surface area (73.2 m²/g) and expose more Mn³⁺/Mn⁴⁺ couples, which improves the redox capacity and electrochemical activity of the composite catalyst and contributes to the process of formaldehyde degradation eventually. Based on the analysis results of in-situ DRFTS, the formation and conversion of formaldehyde on the surface of catalysts were revealed. Formaldehyde is first converted to dioxymethylene (DOM) by surface hydroxyl groups (–OH), and then oxidized to formate species (HCOO⁻) by surface active oxygen, HCOO⁻ is finally oxidized to CO₂ and H₂O. The consumed -OH groups can be compensated from the activation of O₂ via water and surface-active oxygen species reaction. This work paves a new road to utilizing low-grade palygorskite clay as compo-site catalysts for air purification at room temperature.
- low-grade palygorskite clay /
- MnO_x /
- formaldehyde /
- oxidative degradation /
- room temperature

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图 1 MnO_x/PPCI复合催化材料的XRD图谱 (a) 和Raman图谱 (b)

Figure 1. XRD patterns (a) and Raman spectra (b) of MnO_x/PPCI composite catalysts

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图 2 PPCI ((a)~(b))，δ-MnO₂((c)~(e))，33.6 δ-MnO₂/PPCI ((f)~(o)) 的SEM和TEM图像

Figure 2. SEM and TEM images of PPCI ((a)~(b)), δ-MnO₂((c)-(e)) and 33.6 δ-MnO₂/PPCI ((f)-(o))

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图 3 δ-MnO₂和33.6 δ-MnO₂/PPCI的XPS谱图：(a) 总测量扫描；(b) Mn2p；(c)Mn3s；(d) O1s

Figure 3. XPS spectra of δ-MnO₂ and 33.6 δ-MnO₂/PPCI: (a) Total survey scans; (b) Mn2p; (c) Mn3s; (d) O1s

AOS—Average oxidation state

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图 4 催化剂的电化学性能：(a)循环伏安曲线；(b)塔菲尔极化曲线

Figure 4. Electrochemical properties of catalysts: (a) Cyclic voltammograms curves; (b) Tafel polarization curves

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图 5 催化剂去除甲醛的动态效能 (a)、33.6 δ-MnO₂/PPCI长时间动态稳定性测试 (b)、静态效能 (c) 和33.6 δ-MnO₂/PPCI 静态去除甲醛过程中CO₂浓度变化 (d)

Figure 5. Dynamic performance (a), long-term stability of 33.6 δ-MnO₂/PPCI under dynamic test (b), static performance (c) and change of the CO₂ concertration during formaldehyde removal by 33.6 δ-MnO₂/PPCI under static test (d)

C—Concentration

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图 6 催化剂的去除甲醛的一级动力学(a)和二级动力学(b)

Figure 6. First-order kinetic plots (a) and second-order kinetic plots (b) of the catalysts removal formaldehyde

C₀—Initial concentration of formaldehyde; C_t—Outlet concentration of formaldehyde at time t

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图 7 不同催化剂在环境温度下原位DRIFTS光谱：(a) PPCI；(b) δ-MnO₂；(c) 33.6 δ-MnO_2/PPCI；(d) 甲酸盐累积分解速率

Figure 7. In situ DRIFTS spectra of catalysts at room temperature: (a) PPCI; (b) δ-MnO₂; (c) 33.6 δ-MnO₂/PPCI;(d) Accumulation and decomposition rate of HCOO^-

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图 8 δ-MnO₂/PPCI降解甲醛机制

Figure 8. The possible mechanism for formaldehyde removal by δ-MnO₂/PPCI

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表 1 MnO_x/预富集处理的临泽红色低品位凹凸棒石黏土(PPCI)的命名

Table 1. Naming of MnO_x/purifing palygorskite clay rich iron (PPCI)

Sample	Mn/wt%	KMnO₄/g	PPCI/g
6.2 δ-MnO₂/PPCI	6.2	0.55	3
11.6 δ-MnO₂/PPCI	11.6	1.18	3
15.7 δ-MnO₂/PPCI	15.7	1.64	3
23.0 δ-MnO₂/PPCI	23.0	2.57	3
26.7 δ-MnO₂/PPCI	26.7	2.87	3
33.6 δ-MnO₂/PPCI	33.6	4.44	3
35.6 δ-MnO₂/PPCI	35.6	4.85	3

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表 2 MnO₂/PPCI复合材料的比表面积

Table 2. Specific surface area of MnO₂/PPCI

Sample	Surface area/(m²·g⁻¹)
PPCI	64.3
δ-MnO₂	41.4
6.2 δ-MnO₂/PPCI	46.6
11.6 δ-MnO₂/PPCI	52.7
15.7 δ-MnO₂/PPCI	55.4
23.0 δ-MnO₂/PPCI	58.2
26.7 δ-MnO₂/PPCI	67.8
33.6 δ-MnO₂/PPCI	73.2
35.6 δ-MnO₂/PPCI	59.8

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表 3 一级动力学和二级动力学模型的拟合数据

Table 3. Fitting data of the first-order and second-order kinetic models

Order	Parameter	PPCI	δ-MnO₂	15.7 δ-MnO₂/PPCI	33.6 δ-MnO₂/PPCI
First	k₁	−0.0012	−0.039	−0.038	−0.041
First	R²	0.7744	0.8031	0.8453	0.8108
Second	k₂	1.45×10⁻⁴	2.18×10⁻³	1.59×10⁻³	1.86×10⁻³
Second	R²	0.8800	0.9891	0.9946	0.9872
Notes: k₁—Reaction rate constants of first-kinetic model; k₂—Reaction rate constants of second-kinetic model; R²—Correlation.

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