鸡蛋壳负载Co3O4催化剂制备及其N2O分解性能研究

胡晓波; 冯林雁; 武瑞芳; 王永钊; 赵永祥

doi:10.19906/j.cnki.JFCT.2023079

鸡蛋壳负载Co₃O₄催化剂制备及其N₂O分解性能研究

doi: 10.19906/j.cnki.JFCT.2023079

胡晓波^1,,
冯林雁^1,,
武瑞芳^2,,
王永钊^2, ,,
赵永祥^2, ,

1.
忻州师范学院化学系, 山西忻州 034000
2.
山西大学精细化学品教育部工程研究中心, 山西太原 030006

基金项目: 国家自然科学基金(21673132)，山西省基础研究计划（202303021212298），山西省高等学校科技创新项目（2021L458）和忻州师范学院院级项目（2021KY03）资助

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通讯作者:
Tel: 0351-7010588, Fax: 0350-7011688, E-mail: catalyst@sxu.edu.cn

yxzhao@sxu.edu.cn

中图分类号: O643.36
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出版历程
- 收稿日期: 2023-10-11
- 修回日期: 2023-11-20
- 录用日期: 2023-11-24
- 网络出版日期: 2023-12-13

Preparation of eggshell supported Co₃O₄ catalyst and tested for N₂O decomposition

HU Xiaobo^1
,,
FENG Linyan^1
,,
WU Ruifang^2
,,
WANG Yongzhao^{2
, ,},
ZHAO Yongxiang^{2
, ,}

1.
Department of Chemistry, Xinzhou Normal University, Xinzhou 034000, China
2.
Engineering Research Center of Ministry of Education for Fine Chemicals，Shanxi Uniersity, Taiyuan 030006, China

Funds: The project was supported by National Natural Science Foundation of China (21673132), Fundamental Research Program of Shanxi Province (202303021212298), Technological Innovation Programs of Higher Education Institutions in Shanxi (2021L458) and Research Fund of Xinzhou Normal University (2021KY03).

摘要

摘要: 采用废弃的鸡蛋壳作载体，沉积沉淀法制备了一系列不同Co₃O₄含量Co₃O₄/鸡蛋壳催化剂，并在连续流动微反装置上考察了N₂O分解性能。结果表明，当Co₃O₄质量分数为20%时，催化剂表现出优异的N₂O分解性能。在空速10000 h⁻¹和N₂O含量0.1%的条件下，400 ℃可实现N₂O完全转化；其比活性约为Co₃O₄催化剂的4.3倍（反应温度为440 ℃）；同时，该催化剂对原料气中3% O₂、3.3% H₂O和/或2.0×10⁻⁴ NO表现出较强的耐受性和较高的稳定性。分析催化剂的多种表征结果发现，CaCO₃作为鸡蛋壳的主要成分，与活性组分Co₃O₄紧密结合，两者的强相互作用导致20%Co₃O₄/鸡蛋壳催化剂中产生更多的氧空位和Co³⁺；Co₃O₄氧化还原性能得到提高，Co−O键被有效削弱；此外，该强相互作用可提高20%Co₃O₄/鸡蛋壳催化剂表面碱性位点的强度，增大碱性位点数量，更易于转移电子而促进N₂O分解。
- 鸡蛋壳 /
- CaCO₃ /
- Co₃O₄ /
- N₂O /
- 催化分解
Abstract: A series of Co₃O₄/eggshell catalysts with different Co₃O₄ contents were prepared by the deposition-precipitation method using discarded eggshells as supports, and tested for the catalytic reaction of N₂O decomposition on a fixed-bed continuous flow micro-reactor. The activity test results show that the catalyst exhibits higher activity towards N₂O decomposition when the mass fraction of Co₃O₄ is 20%, with a specific activity of 4.3 times to that of pure Co₃O₄ (reaction temperature 440 ℃). At the same time, it shows strong resistance to 3% O₂, 3.3% H₂O and/or 2.0×10⁻⁴ NO in feed. Various characterization results indicate that the predominant composition of eggshell is CaCO₃, which has a close incorporation with Co₃O₄. The strong interaction between CaCO₃ and Co₃O₄ contributes to producing more oxygen vacancies and Co³⁺ in the 20% Co₃O₄/eggshell catalyst. The redox performance of Co₃O₄ is improved, and the Co−O bond is effectively weakened. In addition, it helps to increase the strength and amount of basic sites on the catalyst surface, making it easily transfer electrons and promote N₂O decomposition.
- eggshell /
- CaCO₃ /
- Co₃O₄ /
- N₂O /
- catalytic decomposition

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图 1 材料的XRD谱图

Figure 1 The powder X-ray diffractograms of the materials

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图 2 材料的FT-IR谱图

Figure 2 FT-IR spectra obtained for the materials

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图 3 Co₃O₄ 和20%Co₃O₄/鸡蛋壳催化剂XPS谱图Co 2p (a) 和O 1s (b)

Figure 3 XPS spectra of Co 2p core-level (a) and O 1s core-leve (b) for the Co₃O₄ and 20%Co₃O₄/eggshell catalysts

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图 4 材料的N₂吸附-脱附等温曲线

Figure 4 Nitrogen adsorption-desorption isotherms of the materials

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图 5 催化剂的(HR)-TEM图像

Figure 5 (HR)-TEM images of the catalysts

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图 6 催化剂HADDF-STEM和EDX映射图像

Figure 6 HADDF-STEM and EDX mapping images of the catalyst

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图 7 材料的H₂-TPR谱图

Figure 7 H₂-TPR profiles for the materials

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图 8 催化剂的CO₂-TPD谱图

Figure 8 CO₂-TPD profiles of the catalysts

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图 9 催化剂的O₂-TPD谱图

Figure 9 O₂-TPD profiles of the catalysts

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图 10 催化剂N₂O分解活性

Figure 10 Catalytic performances of the catalysts

Reaction condition: 1.0×10⁻³ N₂O balanced with Ar, GHSV=10000 h⁻¹, 1 atm.

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图 11 20%Co₃O₄/eggshell (a) 和 Co₃O₄ (b)不同原料气中N₂O转化率

Figure 11 N₂O conversion in different feed compositions over 20%Co₃O₄/eggshell (a) and Co₃O₄ (b)

Reaction condition: 1.0×10⁻³ N₂O balanced with Ar, GHSV=10000 h⁻¹, 1 atm.

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图 12 400 ℃时原料气中周期切换杂质气体3% O₂, 3.3% H₂O和2.0×10⁻⁴ NO，20%Co₃O₄/eggshell催化剂N₂O转化率

Figure 12 N₂O conversion over 20%Co₃O₄/eggshell at 400 ℃ changed with time on stream when impurity gases (3% O₂, 3.3% H₂O, 2.0×10⁻⁴ NO) were injected in or cut off from the feed stream

Reaction condition: GHSV=10000 h⁻¹, 1 atm.

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表 1 材料的织构参数

Table 1 The textural parameters for the materials

Material	BET surface area/ (m²·g⁻¹)	Total pore volume/ (cm³·g⁻¹)	Average pore diameter/ nm
CaCO₃	4.3	0.017	8.7
Eggshell	4.5	0.017	8.8
10%Co₃O₄/eggshell	9.4	0.034	12.6
20%Co₃O₄/eggshell	14.5	0.051	14.2
30%Co₃O₄/eggshell	22.8	0.071	17.1
Co₃O₄	34.8	0.158	19.7

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表 2 催化剂不同碱性位点吸附CO₂数量

Table 2 The desorption amount of CO₂for different basic sites on the catalysts

Catalyst	Weak strength basic sites/ (μmol·g⁻¹)	Strong strength basic sites/ (μmol·g⁻¹)	Total basic sites/ (μmol·g⁻¹)
10%Co₃O₄/eggshell	17.4	16.2	33.6
20%Co₃O₄/eggshell	56.6	48.5	105.1
30%Co₃O₄/eggshell	23.5	21.3	44.8
Co₃O₄	39.8	25.1	64.9

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表 3 催化剂不同氧物种脱附O₂数量

Table 3 The desorption amount of O₂ for different oxygen species on the catalysts

Catalyst	Surface oxygen species/(μmol·g⁻¹)	Lattice oxygen species/(μmol·g⁻¹)	Total oxygen species/(μmol·g⁻¹)
10%Co₃O₄/eggshell	23.2	27.8	51.0
20%Co₃O₄/eggshell	47.2	36.1	83.3
30%Co₃O₄/eggshell	25.3	34.9	60.2
Co₃O₄	36.4	11.7	48.1

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参考文献(34)

[1]	KLEGOVA A, PACULTOVA K, KISKA T. Washcoated open-cell foam cobalt spinel catalysts for N₂O decomposition[J]. Mol Catal,2022,533:112754. doi: 10.1016/j.mcat.2022.112754
[2]	ZHAO F L, WANG C Z, WANG D D, et al. Efficient catalytic decomposition of N₂O over Cd-doped NiO in the presence of O₂[J]. Appl Catal A: Gen,2023,649:118946. doi: 10.1016/j.apcata.2022.118946
[3]	BOZORGI B, KARIMI-SABET J, KHADIV-PARSI P. The removal of N₂O from gas stream by catalytic decomposition over Pt-alkali metal/SiO₂[J]. Environ Technol Innovation,2022,26:102344. doi: 10.1016/j.eti.2022.102344
[4]	KONSOLAKIS M. Recent advances on nitrous oxide (N₂O) decomposition over non-noble-metal oxide catalysts: Catalytic performance, mechanistic considerations, and surface chemistry aspects[J]. ACS Catal,2015,5(11):6397−6421. doi: 10.1021/acscatal.5b01605
[5]	赵天琪, 高强, 廖卫平, 等. 掺加Nd和K改性对Co₃O₄催化分解N₂O活性的影响[J]. 燃料化学学报,2019,47(9):1120−1128. doi: 10.1016/S1872-5813(19)30046-5 ZHAO Tianqi, GAO Qiang, LIAO Weiping, et al. Effect of Nd-incorporation and K-modification on catalytic performance of Co₃O₄ for N₂O decomposition[J]. J Fuel Chem Technol,2019,47(9):1120−1128. doi: 10.1016/S1872-5813(19)30046-5
[6]	RICHARDS N, CARTER J H, NOWICKA E, et al. Structure-sensitivity of alumina supported palladium catalysts for N₂O decomposition[J]. Appl Catal B: Environ,2020,264:118501. doi: 10.1016/j.apcatb.2019.118501
[7]	XIONG Y, ZHAO Y M, QI X K, et al. Strong structural modification of Gd to Co₃O₄ for catalyzing N₂O decomposition under simulated real tail gases[J]. Environ Sci Technol,2021,55(19):13335−13344.
[8]	郑珂, 王永钊, 胡晓波, 等. 还原-氧化预处理对Co₃O₄催化分解N₂O性能的影响[J]. 燃料化学学报,2019,47(4):455−463. ZHENG Ke, WANG Yongzhao, HU Xiaobo, et al. Effect of reduction-oxidation pretreatment on the catalytic performance of Co₃O₄ catalyst in N₂O decomposition[J]. J Fuel Chem Technol,2019,47(4):455−463.
[9]	LIANG X L, TANG H L, YANG F F, et al. Ammonia-steam treated FeZSM-5 for direct N₂O decomposition[J]. Microporous Mesoporous Mater,2019,290:109655. doi: 10.1016/j.micromeso.2019.109655
[10]	LIN F, ANDANA T, WU Y Q, et al. Catalytic site requirements for N₂O decomposition on Cu-, Co-, and Fe-SSZ-13 zeolites[J]. J Catal,2021,401:70−80. doi: 10.1016/j.jcat.2021.07.012
[11]	WANG Y Z, ZHENG K, HU X B, et al. Y₂O₃ promoted Co₃O₄ catalyst for catalytic decomposition of N₂O[J]. Mol Catal,2019,470:104−111. doi: 10.1016/j.mcat.2019.04.002
[12]	KIM M J, LEE S J, RYU I S, et al. Catalytic decomposition of N₂O over cobalt based spinel oxides: The role of additives[J]. Mol Catal,2017,442:202−207. doi: 10.1016/j.mcat.2017.05.029
[13]	ZHANG Q L, TANG X S, NING P, et al. Enhancement of N₂O catalytic decomposition over Ca modified Co₃O₄ catalyst[J]. RSC Adv,2015,5(63):51263−51270. doi: 10.1039/C5RA04062K
[14]	IVANOVA Y A, SUTORMINA E F, ISUPOVA L A, et al. Effect of the composition of Ni_xCo_3–xO₄ (x=0–0.9) oxides on their catalytic activity in the low-temperature reaction of N₂O decomposition[J]. Kinet Catal,2018,59(3):357−362. doi: 10.1134/S0023158418030072
[15]	WANG Y Z, HU X B, ZHENG K, et al. Effect of SnO₂ on the structure and catalytic performance of Co₃O₄ for N₂O decomposition[J]. Catal Commun,2018,111:70−74. doi: 10.1016/j.catcom.2018.04.004
[16]	HU X B, WANG Y Z, WU R F, et al. Effects of zirconia crystal phases on the catalytic decomposition of N₂O over Co₃O₄/ZrO₂ catalysts[J]. Appl Surf Sci,2020,514:145892. doi: 10.1016/j.apsusc.2020.145892
[17]	GRZYBEK G, STELMACHOWSKI P, GUDYKA S, et al. Strong dispersion effect of cobalt spinel active phase spread over ceria for catalytic N₂O decomposition: The role of the interface periphery[J]. Appl Catal B: Environ,2016,180:622−629. doi: 10.1016/j.apcatb.2015.07.027
[18]	KLEGOVÁ A, PACULTOVÁ K, FRIDRICHOVÁ D, et al. Cobalt oxide catalysts on commercial supports for N₂O decomposition[J]. Chem Eng Technol,2017,40:981−990. doi: 10.1002/ceat.201600628
[19]	YU H B, WANG X P, LI Y. Strong impact of cobalt distribution on the activity for Co₃O₄/CaCO₃ catalyzing N₂O decomposition[J]. Catal Today,2020,339:274−280. doi: 10.1016/j.cattod.2018.10.036
[20]	HU X B, WANG Y Z, WU R F, et al. Graphitic carbon nitride-supported cobalt oxides as a potential catalyst for decomposition of N₂O[J]. Appl Surf Sci,2021,538:148157. doi: 10.1016/j.apsusc.2020.148157
[21]	LACA A, LACA A, DÍAZ M. Eggshell waste as catalyst: A review[J]. J Environ Manage,2017,197:351−359. doi: 10.1016/j.jenvman.2017.03.088
[22]	YUSUFF A S, ADENIYI O D, AZEEZ S O, et al. Synthesis and characterization of anthill-eggshell-Ni-Co mixed oxides composite catalyst for biodiesel production from waste frying oil[J]. Biofuels Bioprod Biorefin,2019,13(1):37−47. doi: 10.1002/bbb.1914
[23]	GUO Y L, YANG D P, LIU M H, et al. Enhanced catalytic benzene oxidation over a novel waste-derived Ag/eggshell catalyst[J]. J Mater Chem A,2019,7(15):8832−8844. doi: 10.1039/C8TA10822F
[24]	LI Z H, YANG D P, CHEN Y S, et al. Waste eggshells to valuable Co₃O₄/CaCO₃ materials as efficient catalysts for VOCs oxidation[J]. Mol Catal,2020,483:110766. doi: 10.1016/j.mcat.2020.110766
[25]	郑丽, 李和健, 徐秀峰. 碳球为模板水热合成Mg-Co复合氧化物及其催化分解N₂O[J]. 燃料化学学报(中英文),2018,46(5):569−577. doi: 10.1016/S1872-5813(18)30024-0 ZHENG Li, LI Hejian, XU Xiufeng. Catalytic decomposition of N₂O over Mg-Co composite oxides hydrothermally prepared by using carbon sphere as template[J]. J Fuel Chem Technol,2018,46(5):569−577. doi: 10.1016/S1872-5813(18)30024-0
[26]	SUN J R, SONG A L, TIAN Y, et al. Unravelling the effect of alkali metal deposition on Co₃O₄ for catalytic decomposition of N₂O[J]. ChemCatChem,2023,15:1−10.
[27]	李和健, 郑丽, 赵天琪, 等. 水热合成Co₃O₄的制备参数调变及其催化分解N₂O性能[J]. 燃料化学学报,2018,46(6):717−724. doi: 10.1016/S1872-5813(18)30031-8 LI Hejian, ZHENG Li, ZHAO Tianqi, et al. Effect of preparation parameters on the catalytic performance of hydrothermally synthesized Co₃O₄ in the decomposition of N₂O[J]. J Fuel Chem Technol,2018,46(6):717−724. doi: 10.1016/S1872-5813(18)30031-8
[28]	YU H B, WANG X P, WU, X X, et al. Promotion of Ag for Co₃O₄ catalyzing N₂O decomposition under simulated real reaction conditions[J]. Chem Eng J,2018,334:800−806. doi: 10.1016/j.cej.2017.10.079
[29]	刘晓丽, 王永钊, 赵永祥. Sr掺杂羟基磷灰石负载Co₃O₄催化N₂O分解[J]. 燃料化学学报,2021,49(8):1190−1200. LIU Xiaoli, WANG Yongzhao, ZHAO Yongxiang. Co₃O₄ supported on Sr doped hydroxyapatite as catalysts for N₂O catalytic decomposition[J]. J Fuel Chem Technol,2021,49(8):1190−1200.
[30]	DONG N, CHEN M Y, YE Q, et al. Promotional effect of cobalt doping on catalytic performance of cryptomelane-type manganese oxide in toluene oxidation[J]. J Environ Sci,2023,126:263−274. doi: 10.1016/j.jes.2022.03.024
[31]	ZHANG C, ZHANG Z P, SUI C, et al. Catalytic decomposition of N₂O over Co-Ti oxide catalysts: Interaction between Co and Ti oxide[J]. ChemCatChem,2016,8(12):2155−2164. doi: 10.1002/cctc.201600231
[32]	HU X B, WANG Y Z, WU R F, et al. N-doped Co₃O₄ catalyst with a high efficiency for the catalytic decomposition of N₂O[J]. Mol Catal,2021,509:111656. doi: 10.1016/j.mcat.2021.111656
[33]	窦喆, 张海杰, 潘燕飞, 等. N₂O在钾改性Cu-Co尖晶石型复合氧化物上的催化分解[J]. 燃料化学学报,2014,42(2):238−245. doi: 10.1016/S1872-5813(14)60016-5 DOU Zhe, ZHANG Haijie, PAN Yanfei, et al. Catalytic decomposition of N₂O over potassium-modified Cu-Co spinel oxides[J]. J Fuel Chem Technol,2014,42(2):238−245. doi: 10.1016/S1872-5813(14)60016-5
[34]	赵婉君, 李潇, 党慧, 等. 负载型Pd-Cu催化剂的制备及富氢气氛下CO优先氧化性能[J]. 高等学校化学学报(中英文),2022,43(3):20210754. ZHAO Wanjun, LI Xiao, Dang Hui, et al. Preparation of supported Pd-Cu catalyst and its preferential oxidation of CO under hydrogen-rich atmosphere[J]. Chem J Chin Univ,2022,43(3):20210754.

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鸡蛋壳负载Co₃O₄催化剂制备及其N₂O分解性能研究

doi: 10.19906/j.cnki.JFCT.2023079

通讯作者:
Tel: 0351-7010588, Fax: 0350-7011688, E-mail: catalyst@sxu.edu.cn

yxzhao@sxu.edu.cn

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Preparation of eggshell supported Co₃O₄ catalyst and tested for N₂O decomposition

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