Effect of manganese modification on the low-temperature formaldehyde oxidation performance of ZIF-67 derived Co3O4
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摘要: 针对ZIF-67衍生Co3O4催化剂低温甲醛氧化性能不佳的问题，采用锰（Mn）对Co3O4催化剂进行改性以提升其低温甲醛氧化性能。活性评价结果表明，相比于未改性的Co3O4催化剂，Mn改性后的Mn-Co3O4催化剂甲醛氧化活性显著提升，在118 ℃下即可实现90%的甲醛转化率（进口甲醛浓度为98.16 mg/m3，空速为60000 mL /(gcat·h)）。XRD、Raman和BET结果显示，Mn改性后催化剂的结晶度降低，缺陷增加，比表面积增大，这有利于反应物分子的吸附和活性位点的暴露。XPS、H2-TPR和O2-TPD表征结果表明，Mn-Co间存在的强相互作用显著改善了Mn-Co3O4催化剂的低温氧化还原性能和氧活化能力，使其具有更加丰富的Co3+和表面吸附氧物种。最终，这些因素共同促进了Mn-Co3O4催化剂对甲醛的降解。此外，in-situ DRIFTS结果表明，亚甲二氧基和甲酸盐物种是甲醛在Mn-Co3O4催化剂上催化氧化的主要中间物种。Abstract: In consideration of the inferior performance of ZIF-67 derived Co3O4 catalyst in the low-temperature formaldehyde oxidation, manganese was utilized to modify Co3O4 catalyst. The results showed that the Mn-Co3O4 catalyst exhibited the superior HCHO oxidation activity and achieved 90% HCHO conversion at a WHSV of 60000 mL/(gcat·h) and inlet HCHO concentration of 98.16 mg/m3 at 118 ℃. XRD, Raman and BET results demonstrated that the Mn-Co3O4 catalyst possessed lower crystallinity, more defects and specific surface area, which was conducive to the adsorption of reactants and exposure of more active sites. XPS, H2-TPR and O2-TPD results indicated that the strong interaction between Mn and Co species prominently improved the low temperature reducibility and O2 activation performance of Mn-Co3O4 catalyst, which endowed it with more abundant Co3+ and surface-adsorbed oxygen species. Therefore, the Mn-Co3O4 catalyst exhibited superior HCHO oxidation performance. Based on in-situ DRIFTS results, dioxymethylene and formate species were recognized as the main reaction intermediates of HCHO oxidation over the Mn-Co3O4 catalyst.
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Key words:
- formaldehyde /
- catalytic oxidation /
- ZIF-67 /
- Mn-Co oxide
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图 1 Co3O4和Mn-Co3O4催化剂的甲醛氧化起燃曲线
Figure 1 Light-off profiles of HCHO oxidation over Co3O4 and Mn-Co3O4 catalysts
图 2 Mn-Co3O4催化剂的甲醛氧化稳定性测试
Figure 2 Stability test of Mn-Co3O4 catalyst for HCHO oxidation at 120 ℃
图 5 Co3O4和Mn-Co3O4催化剂的氮气吸附-脱附等温线(a)和孔径分布(b)
Figure 5 N2 adsorption-desorption isotherms (a) and pore size distributions (b) of Co3O4 and Mn-Co3O4 catalysts
图 6 不同催化剂前驱体和催化剂的SEM照片
Figure 6 SEM images of various catalyst precursors and catalysts
(a): ZIF-67; (b): Mn-ZIF-67; (c): Co3O4; (d): Mn-Co3O4; (e): EDS-mapping images of Mn-Co3O4
图 8 Co3O4和Mn-Co3O4催化剂的H2-TPR谱图
Figure 8 H2-TPR patterns of Co3O4 and Mn-Co3O4 catalysts
图 9 Co3O4和Mn-Co3O4催化剂的O2-TPD谱图
Figure 9 O2-TPD patterns of Co3O4 and Mn-Co3O4 catalysts
图 10 Mn-Co3O4催化剂的原位红外光谱谱图
Figure 10 In-situ DRIFTS spectra of Mn-Co3O4 catalyst for HCHO oxidation at 120 ℃
图 11 甲醛在Mn-Co3O4催化剂上可能的氧化路径示意图
Figure 11 Possible HCHO oxidation pathway over Mn-Co3O4 catalyst
表 1 Co3O4和Mn-Co3O4催化剂的结构参数
Table 1 Properties of Co3O4 and Mn-Co3O4 catalysts
Sample Crystallite size /nm Lattice parameter /Å SBET /(m2·g−1) Pore volume /(cm3·g−1) Average pore diameter /nm Co3O4 21.5 8.073 39.75 0.33 33.38 Mn-Co3O4 16.4 8.085 59.38 0.39 26.00 
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表 2 Co3O4和Mn-Co3O4催化剂的XPS表征和表面吸附氧脱附量
Table 2 XPS results and desorption amounts of surface-adsorbed oxygen of Co3O4 and Mn-Co3O4 catalysts
Sample Co3+/Co2+ Mn4+/Mn Oα/Oβ Desorption amounts
of surface-adsorbed
oxygen /(μmol·g−1)Co3O4 0.55 − 0.36 140.23 Mn-Co3O4 0.74 0.43 0.48 168.80
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