富含零价钴活性位点的钴氮碳/活性炭设计及甲醛催化氧化应用研究

doi:10.11949/0438-1157.20230402

化工学报 ›› 2023, Vol. 74 ›› Issue (8): 3342-3352.DOI: 10.11949/0438-1157.20230402

• 催化、动力学与反应器 • 上一篇下一篇

富含零价钴活性位点的钴氮碳/活性炭设计及甲醛催化氧化应用研究

李凯旋¹(), 谭伟¹, 张曼玉², 徐志豪¹, 王旭裕²^,⁴(), 纪红兵¹^,²^,³^,⁴^,⁵()

^1.广东工业大学轻工化工学院，广东广州 510006
^2.江苏科技大学环境化学与工程学院，江苏镇江 212100
^3.浙江工业大学化学工程学院，绿色石化与轻烃转化研究院，浙江杭州 310014
^4.中山大学惠州研究院，广东惠州 516081
^5.广东龙湖科技股份有限公司，广东汕头 515041

收稿日期:2023-04-26 修回日期:2023-08-15 出版日期:2023-08-25 发布日期:2023-10-18
通讯作者: 王旭裕,纪红兵
作者简介:李凯旋（1998—），男，硕士研究生，1227423220@qq.com
基金资助:
广东省“珠江人才计划”本土创新科研团队项目(2017BT01C102);广东省重点领域研发计划项目(2019B110206002);广东省自然科学基金面上项目(2022A1515011791);广东省植物资源生物炼制重点实验室开放基金项目(2021GDKLPRB10);汕头市精细化工企业引进科技领军人才团队及进口替代技术攻关专项资金项目(211210147160629)

Design of cobalt-nitrogen-carbon/activated carbon rich in zero valent cobalt active site and application of catalytic oxidation of formaldehyde

Kaixuan LI¹(), Wei TAN¹, Manyu ZHANG², Zhihao XU¹, Xuyu WANG²^,⁴(), Hongbing JI¹^,²^,³^,⁴^,⁵()

^1.School of Chemical Engineering and Light Industry, Guangdong University of Technology, Guangzhou 510006, Guangdong, China
^2.School of Environmental and Chemical Engineering, Jiangsu University of Science and Technology, Zhenjiang 212100, Jiangsu, China
^3.Institute of Green Petroleum Processing and Light Hydrocarbon Conversion, College of Chemical Engineering, Zhejiang University of Technology, Hangzhou 310014, Zhejiang, China
^4.Huizhou Research Institute of Sun Yat-sen University, Huizhou 516081, Guangdong, China
^5.Guangdong Longhu SCI. & Tech. Company Limited, Shantou 515041, Guangdong, China

Received:2023-04-26 Revised:2023-08-15 Online:2023-08-25 Published:2023-10-18
Contact: Xuyu WANG, Hongbing JI

摘要/Abstract

摘要：

具有低成本、高效率的挥发性有机化合物（VOC）氧化催化剂对于环境保护至关重要。钴-氮-碳（CoNC）材料由于其高度分散的Co与氮配位形成CoN _x 后可较好地进行氧物种的活化，在光催化、电催化氧化领域表现出超高的催化活性。但目前将CoNC催化剂应用于甲醛催化氧化尚未得到广泛研究。合成了钴氮碳/活性炭（CoNC/AC）系列催化剂，通过控制热解温度调节CoNC/AC表面的化学组成和活性位点分布，在700℃下获得的CoNC/AC催化剂在25℃下可实现70 mg·m^-3 HCHO 95%的转化率，3300 h稳定性测试发现催化剂HCHO转化率依然稳定在90%左右。与贵金属相比，过渡金属CoNC/AC催化剂具有出色的HCHO去除能力和低成本的优势。此外，通过相关性分析和原位红外揭示了CoNC/AC催化剂上的HCHO去除机制，表明HCHO分子可以与吸附在0价Co位点的O₂反应，在室温下生成CO₂和H₂O（CH₂O→HCHO₂→CHO₂→CO₂）。

关键词: 催化剂, 甲醛去除, 氧化, N掺杂碳, 固定床

Abstract:

Low-cost, high-efficiency volatile organic compound (VOC) oxidation catalysts are crucial for environmental protection. Cobalt-nitrogen-carbon (CoNC) materials are able to activate oxygen species effectively, thanks to the highly dispersed Co coordinated with nitrogen to form CoN _x . This property makes CoNC a promising candidate in the fields of photocatalytic and electrocatalytic oxidation. Despite this, the application of CoNC catalysts in the catalytic oxidation of formaldehyde has not been extensively studied. In this study, a series of cobalt-nitrogen-carbon/activated carbon (CoNC/AC) catalysts were synthesized by controlling the pyrolysis temperature to tailor the chemical composition and active site distribution on the CoNC/AC surface. The CoNC/AC catalyst obtained at 700℃ showed a 95% conversion rate of 70 mg·m^-3 HCHO at 25℃, and stability tests over 3300 h demonstrated that the HCHO conversion rate remained steady at around 90%. Compared to noble metals, the transition metal CoNC/AC catalyst possesses superior HCHO removal capability and cost-effectiveness. Furthermore, the HCHO removal mechanism on the CoNC/AC catalyst was elucidated through correlation analysis and in situ infrared spectroscopy. The results indicated that the HCHO molecule can react with O₂ adsorbed on the zero-valent Co site to generate CO₂ and H₂O (CH₂O→HCHO₂→CHO₂→CO₂) at ambient temperature.

Key words: catalyst, HCHO removal, oxidation, N-doped C, fixed-bed

中图分类号:

TQ 426.81

李凯旋, 谭伟, 张曼玉, 徐志豪, 王旭裕, 纪红兵. 富含零价钴活性位点的钴氮碳/活性炭设计及甲醛催化氧化应用研究[J]. 化工学报, 2023, 74(8): 3342-3352.

Kaixuan LI, Wei TAN, Manyu ZHANG, Zhihao XU, Xuyu WANG, Hongbing JI. Design of cobalt-nitrogen-carbon/activated carbon rich in zero valent cobalt active site and application of catalytic oxidation of formaldehyde[J]. CIESC Journal, 2023, 74(8): 3342-3352.

图/表 11

图1 x-CoNC/AC (x=300, 500, 700, 900)的甲醛活性测试和700-CoNC/AC的稳定性测试

Fig.1 The activity test of x-CoNC/AC (x=300, 500, 700, 900) and stability test of 700-CoNC/AC in HCHO catalytic oxidation

图2 CoNC/AC催化剂的微观表征

Fig.2 Microscopic characterization of CoNC/AC

图3 x-CoNC/AC (x=300, 500, 700, 900)的N2等温吸脱附曲线和孔径分布

Fig.3 N2 adsorption-desorption curves and pore size distributions of x-CoNC/AC (x=300, 500, 700, 900)

表1 x-CoNC/AC （x=300， 500， 700， 900）的比表面积和孔结构参数

Table 1 Specific surface areas and pore structures of x-CoNC/AC （x=300， 500， 700， 900）

Simple	BET surface area/ (m²·g^-1)	Pore volume/ (cm³·g^-1)	Pore size /nm
300-CoNC/AC	43.26	0.15	9.45
500-CoNC/AC	37.87	0.07	6.82
700-CoNC/AC	205.89	0.24	6.51
900-CoNC/AC	319.23	0.17	4.30

图4 x-CoNC/AC (x=300, 500, 700, 900)和AC的X射线衍射谱图

Fig.4 XRD patterns of x-CoNC/AC (x=300, 500, 700, 900) and AC

图5 x-CoNC/AC (x=300, 500, 700, 900)的XPS谱图

Fig.5 XPS spectra of x-CoNC/AC (x=300, 500, 700, 900)

表2 x-CoNC/AC （x=300， 500， 700， 900）的相关功能活性位点的相对数量

Table 2 Relative amount of functional active sites in x-CoNC/AC （x=300， 500， 700， 900）

种类	相对数量/%
种类	300-CoNC/ AC	500-CoNC/AC	700-CoNC/AC	900-CoNC/AC
C $\overset{}{̿}$ O	49.9	59.9	59.4	37.6
C—O	19.2	10.5	29.7	28.8
O—C $\overset{}{̿}$ O	30.9	29.6	10.9	33.7
吡啶N	17.7	40.0	35.0	16.3
吡咯N	45.9	26.0	19.6	0.1
氮氧化物	18.8	16.4	23.1	30.9
石墨N	17.6	17.6	22.3	52.7
Co (0)	0	3.9	11.0	44.9
Co—O	7.4	35.1	47.9	22.6
Co—N _x	52.3	31.7	19.0	20.5
satellites	40.3	29.3	22.1	11.9

表2 x-CoNC/AC （x=300， 500， 700， 900）的相关功能活性位点的相对数量

Table 2 Relative amount of functional active sites in x-CoNC/AC （x=300， 500， 700， 900）

种类	相对数量/%
种类	300-CoNC/ AC	500-CoNC/AC	700-CoNC/AC	900-CoNC/AC
C $\overset{}{̿}$ O	49.9	59.9	59.4	37.6
C—O	19.2	10.5	29.7	28.8
O—C $\overset{}{̿}$ O	30.9	29.6	10.9	33.7
吡啶N	17.7	40.0	35.0	16.3
吡咯N	45.9	26.0	19.6	0.1
氮氧化物	18.8	16.4	23.1	30.9
石墨N	17.6	17.6	22.3	52.7
Co (0)	0	3.9	11.0	44.9
Co—O	7.4	35.1	47.9	22.6
Co—N _x	52.3	31.7	19.0	20.5
satellites	40.3	29.3	22.1	11.9

图6 x-CoNC/AC (x=300, 500, 700, 900)的红外光谱图

Fig.6 FTIR spectrums of x-CoNC/AC (x=300, 500, 700, 900)

图7 CoNC/AC催化剂中活性位点、SBET、孔容、孔径与催化效率的相关性

Fig.7 Correlation between active sites of catalysts, SBET, pore volume, pore size and conversion in CoNC/AC catalysts

图8 在25℃和O2+HCHO+He气氛下催化剂随时间变化的原位红外光谱

Fig.8 In-situ DRIFTS spectra of O2 + HCHO + He gas mixture adsorption for 60 min at 25℃

图9 700-CoNC/AC催化剂上的甲醛降解机理

Fig.9 Schematic illustrations of degradation mechanism of formaldehyde over 700-CoNC/AC catalyst

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富含零价钴活性位点的钴氮碳/活性炭设计及甲醛催化氧化应用研究

Design of cobalt-nitrogen-carbon/activated carbon rich in zero valent cobalt active site and application of catalytic oxidation of formaldehyde

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