沉淀剂对Co3O4催化分解N2O的性能影响

doi:10.16085/j.issn.1000-6613.2023-0579

摘要/Abstract

摘要：

以乙酸钴为钴源采用水热法制备了Co₃O₄催化剂，通过X射线衍射仪、傅里叶变换红外光谱仪、透射电子显微镜、扫描电子显微镜、N₂物理吸附脱附测试、H₂程序升温还原、氧的程序升温脱附和X射线光电子能谱等表征手段对Co₃O₄催化剂的物理化学性质进行表征，在固定床微型反应器中评价催化剂催化分解N₂O活性，考察了不同沉淀剂（氢氧化钠、碳酸钠、碳酸氢钠、尿素、碳酸铵、氨水）对催化剂催化分解N₂O的性能影响。结果表明，水热法制备的Co₃O₄催化剂均为尖晶石结构，不同沉淀剂影响催化剂形貌、氧化还原性能和催化分解N₂O活性；含有钠离子沉淀剂制备而得的催化剂活性高于其他催化剂，其促进了Co³⁺到Co²⁺的还原过程，影响了钴离子化学环境，提高了给电子能力，弱化了催化剂中的Co—O键，加快了反应过程中氧空位的再生，进而提高了自身的催化活性；其中含少量Na离子的Co₃O₄-NaOH催化剂具有较强的氧化还原性，O_ads/O_latt较大，表面吸附氧数量多，N₂O分解温度较低，在反应气体组成为0.88% O₂、0.65% N₂O，N₂为平衡气的（流量为80mL/min）条件下，T₁₀和T₉₅分别为330℃和470℃。

关键词: 沉淀剂, 氧化亚氮, 四氧化三钴, 钠离子, 氧空位

Abstract:

The Co₃O₄ composite metal oxides were prepared by the hydrothermal method using cobalt acetate as the cobalt source. The physicochemical properties of the catalysts were characterized by XRD, FTIR, TEM, SEM, BET, H₂-TPR, O₂-TPD and XPS. The catalyst catalytic decomposition activity of N₂O was evaluated in a fixed-bed microreactor, and the effect of precipitants (NaOH、 Na₂CO₃、 NaHCO₃、 H₂NCONH₂、 CH₈N₂O₃、 NH₃·H₂O) on the catalytic decomposition performance of N₂O was investigated. The results showed that the Co₃O₄ catalysts prepared by the hydrothermal method were all of spinel structure, and different precipitating agents affected the catalyst morphology, redox performance and catalytic decomposition N₂O activity. The activity of the catalysts prepared with sodium precipitant was higher than that of other catalysts because it promoted the reduction process of Co³⁺ to Co²⁺, influenced the chemical environment of cobalt ions, improved the electron donating capability, weakened the Co—O bond in the catalyst, and accelerated the regeneration of oxygen vacancies during the catalytic reaction. The Co₃O₄-NaOH catalyst, which contained a small amount of Na ions, had a strong redox ability, a large O_ads/O_latt ratio, resulting in a large amount of oxygen adsorbed on the surface, and a low N₂O decomposition temperature. Under the conditions of the reaction gas composition of 0.88% O₂, 0.65% N₂O, and N₂ as equilibrium gas (flow rate of 80mL/min), T₁₀ and T₉₅ were 330℃ and 470℃, respectively.

Key words: precipitating agent, nitrous oxide, tricobalt tetraoxide, sodium ion, oxygen vacancy

中图分类号:

TQ426.6

孙巾茹, 宋傲磊, 赵明新, 赵田田, 王虹, 柯明. 沉淀剂对Co₃O₄催化分解N₂O的性能影响[J]. 化工进展, 2024, 43(4): 1823-1831.

SUN Jinru, SONG Aolei, ZHAO Mingxin, ZHAO Tiantian, WANG Hong, KE Ming. Effect of precipitating agent on the performance of Co₃O₄-catalyzed decomposition of N₂O[J]. Chemical Industry and Engineering Progress, 2024, 43(4): 1823-1831.

图/表 11

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催化剂	2θ/(°)	a₀/Å	V/nm³	FWHM /(°)	D_XRD/nm	比表面积 /m²∙g^-1
Co₃O₄-NaOH	37.095	8.027	517.1	0.186	46.52	25.2
Co₃O₄-Na₂CO₃	37.154	8.014	514.8	0.179	47.96	17.4
Co₃O₄-NaHCO₃	37.057	8.035	518.7	0.148	58.79	25.9
Co₃O₄-尿素	37.002	8.046	520.9	0.149	58.90	21.4
Co₃O₄-碳酸铵	37.040	8.038	519.3	0.148	58.94	18.6
Co₃O₄-氨水	37.036	8.039	519.5	0.147	59.38	15.7

催化剂	2θ/(°)	a₀/Å	V/nm³	FWHM /(°)	D_XRD/nm	比表面积 /m²∙g^-1
Co₃O₄-NaOH	37.095	8.027	517.1	0.186	46.52	25.2
Co₃O₄-Na₂CO₃	37.154	8.014	514.8	0.179	47.96	17.4
Co₃O₄-NaHCO₃	37.057	8.035	518.7	0.148	58.79	25.9
Co₃O₄-尿素	37.002	8.046	520.9	0.149	58.90	21.4
Co₃O₄-碳酸铵	37.040	8.038	519.3	0.148	58.94	18.6
Co₃O₄-氨水	37.036	8.039	519.5	0.147	59.38	15.7

催化剂	原子含量/%
催化剂	Na	O	Co
Co₃O₄-NaOH	0.4	53.1	46.5
Co₃O₄-Na₂CO₃	9.1	48.9	42.0
Co₃O₄-NaHCO₃	6.5	53.4	40.1

催化剂	原子含量/%
催化剂	Na	O	Co
Co₃O₄-NaOH	0.4	53.1	46.5
Co₃O₄-Na₂CO₃	9.1	48.9	42.0
Co₃O₄-NaHCO₃	6.5	53.4	40.1

催化剂	α		β		总面积 /10^-6	面积比(β/α)
催化剂	峰位 /℃	面积 /10^-6	峰位 /℃	面积 /10^-6	总面积 /10^-6	面积比(β/α)
Co₃O₄-NaOH	350	1.61	397	5.10	6.71	3.2
Co₃O₄-Na₂CO₃	337	1.83	441	5.72	7.55	3.1
Co₃O₄-NaHCO₃	353	1.52	441	4.69	6.21	3.1
Co₃O₄-尿素	352	1.16	402	3.48	4.64	3.0
Co₃O₄-碳酸铵	358	1.08	405	3.26	4.34	3.0
Co₃O₄-氨水	359	0.68	408	2.10	2.78	3.1

沉淀剂对Co₃O₄催化分解N₂O的性能影响

Effect of precipitating agent on the performance of Co₃O₄-catalyzed decomposition of N₂O

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催化剂	Co 2p_3/2结合能/eV		Co²⁺/Co³⁺	O 1s结合能/eV		O_ads/O_latt
催化剂	Co²⁺	Co³⁺	Co²⁺/Co³⁺	O_ads	O_latt	O_ads/O_latt
Co₃O₄-NaOH	780.59	778.89	0.53	531.01	529.71	0.68
Co₃O₄-Na₂CO₃	780.61	778.91	0.53	531.02	529.52	0.79
Co₃O₄-NaHCO₃	780.63	778.93	0.52	531.02	529.52	0.62
Co₃O₄-尿素	780.71	779.01	0.49	531.12	529.82	0.59
Co₃O₄-碳酸铵	780.71	779.01	0.47	531.12	529.82	0.55
Co₃O₄-氨水	780.72	779.02	0.46	531.12	529.82	0.45

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催化剂	T₁₀/℃	T₉₅/℃
Co₃O₄-NaOH	330	470
Co₃O₄-Na₂CO₃	398	462
Co₃O₄-NaHCO₃	418	491
Co₃O₄-尿素	378	561
Co₃O₄-碳酸铵	400	580
Co₃O₄-氨水	411	630

催化剂	T₁₀/℃	T₉₅/℃
Co₃O₄-NaOH	330	470
Co₃O₄-Na₂CO₃	398	462
Co₃O₄-NaHCO₃	418	491
Co₃O₄-尿素	378	561
Co₃O₄-碳酸铵	400	580
Co₃O₄-氨水	411	630