过渡金属基氮掺杂炭的构筑及其脱硫性能研究

doi:10.11949/0438-1157.20251078

摘要/Abstract

摘要：

H₂S是一种剧毒、强腐蚀性的气体，其高效脱除对工业生产和人居环境具有重要意义。本研究基于过渡金属基氮掺杂炭（TM-NPC）催化剂在脱硫方面的应用前景，以葡萄糖酸盐为碳源和金属前驱体，草酸铵为氮源，碳酸氢钠为活化剂，通过一步热解制备了系列TM-NPC，考察了碳酸氢钠、热解温度、过渡金属类型对脱硫性能的影响，借助扫描电子显微镜（SEM）、X射线光电子能谱（XPS）、比表面积分析仪（BET）和傅里叶变换红外光谱仪（FTIR）对催化剂进行了理化性质分析。结果表明，在葡萄糖酸盐：草酸铵：碳酸氢钠配比为1：2：5、热解温度为800 ℃时，所获得的Cu-NPC脱硫性能最佳，且明显优于Fe-NPC和Mn-NPC，发现与氮气相比，氧气环境对于H₂S的脱除具有极大促进作用。脱硫持久性实验表明，催化剂可在常温条件保持高效脱硫能力长达800 min，吸附量可达到430.5 mg/g，并发现Cu位点是Cu-NPC实现高效脱硫的关键活性位。综上，本研究为开发新型高效TM-NPC催化剂提供了新思路，促进了H₂S资源化转化及利用。

关键词: 催化, 活性炭, 纳米材料, 脱硫, 多相反应

Abstract:

As a toxic and corrosive gas, the efficient removal of H₂S is significant for industrial production and living environment. Given the promising application prospects of transition metal-based nitrogen-doped carbon (TM-NPC) in desulfurization, a series of TM-NPC catalysts via one-step pyrolysis method were synthesized using glucose salts as both carbon source and metal precursor, ammonium oxalate as nitrogen source, and sodium bicarbonate as activating agent. The effects of sodium bicarbonate dosage, pyrolysis temperature, and transition metal on the desulfurization performance of TM-NPC were investigated. Physicochemical properties of catalysts were analyzed by scanning electron microscopy (SEM), X-ray photoelectron spectroscopy (XPS), Brunauer-Emmett-Teller (BET), and Fourier transform infrared spectroscopy (FTIR). The results indicated that the optimal mass ratio of glucose salts: ammonium oxalate: sodium bicarbonate was 1:2:5, and the pyrolysis temperature was 800 °C. Under the above conditions, the obtained Cu-NPC exhibited the best desulfurization performance compared to Fe-NPC and Mn-NPC. Furthermore, compared to nitrogen atmosphere, the oxygen environment significantly enhanced H₂S removal, and the desulfurization persistence test showed that Cu-NPC can maintain high-efficiency desulfurization ability within 800 min, accompanied by the sulfur capacity of 430.5 mg/g. Notably, it can be confirmed that the crucial active site in Cu-NPC was Cu metal sites for achieving high-efficiency desulfurization. In conclusion, this study provides a new idea for the development of novel and efficient TM-NPC, facilitating the resource transformation and utilizing of H₂S.

Key words: Catalysis, activated carbon, nanomaterials, desulfurization, multiphase reaction

中图分类号:

X701

靳常洲, 尹梦阳, 王昊琛, 宋佳, 王竞侦, 马双龙, 黄岩. 过渡金属基氮掺杂炭的构筑及其脱硫性能研究[J]. 化工学报, DOI: 10.11949/0438-1157.20251078.

Chang'zhou JIN, Meng'yang YIN, Hao'chen WANG, Jia SONG, Jing'zhen WANG, Shuang'long MA, Yan HUANG. Construction of Transition Metal-based Nitrogen-doped Carbon and Their Desulfurization Performance[J]. CIESC Journal, DOI: 10.11949/0438-1157.20251078.

图/表 13

图1 碳酸氢钠用量对Cu-NPC脱硫性能的影响

Figure 1 Effect of NaHCO3 dosage on the desulfurization performance of Cu-NPC

图2 不同配比Cu-NPC的SEM图：1：2：1（a）；1：2：3（b）；1：2：5（c）；1：2：7（d）

Figure 2 SEM images of Cu-NPC with different ratios: 1:2:1 (a); 1:2:3 (b); 1:2:5 (c); 1:2:7 (d)

图3 热解温度对Cu-NPC脱硫性能（a）和吸附量（b）的影响

Figure 3 Effect of pyrolysis temperature on desulfurization performance (a) and adsorption capacity (b) of Cu-NPC

图4 不同热解温度Cu-NPC的SEM图：700 ℃（a）；800 ℃（b）；900 ℃（c）；氮气吸附-脱附等温线（e）和N 1s谱图（f）

Figure 4 SEM images of Cu-NPC obtained at different pyrolysis temperature: 700 ℃ (a); 800 ℃ (b); 900 ℃ (c); Nitrogen adsorption-desorption isotherms (e) and N 1s XPS spectra (f) of Cu-NPC at different pyrolysis temperatures

表1 不同热解温度Cu-NPC的比表面积、N含量和Cu含量分布

Table 1 Specific surface area， N and Cu contents of Cu-NPC obtained at different pyrolysis temperatures

煅烧温度	比表面积 (m²/g)	总孔体积 (cm³/g)	微孔体积 (cm³/g)	孔径 (nm)	N (at.%)	Cu (at.%)
700 ℃	197.38	0.3892	0.0483	7.8878	5.52	3.42
800 ℃	380.79	0.4732	0.1309	4.9710	3.48	2.11
900 ℃	378.26	0.4670	0.1552	4.9383	2.15	0.71

图5 不同金属掺杂TM-NPC脱硫性能（a）和吸附量（b）

Figure 5 Desulfurization performance (a) and adsorption capacity (b) for TM-NPC loading with different metals

图6 不同金属掺杂TM-NPC的SEM图：Cu-NPC（a）；Fe-NPC（b）；Mn-NPC（c）；不同金属掺杂TM-NPC的XPS谱图：Cu-NPC的 Cu 2p（d）及N 1s（g）谱图；Fe-NPC的Fe 2p（e）及N 1s（h）谱图；Mn-NPC的Mn 2p（f）及N 1s（i）谱图

Figure 6 SEM images of TM-NPC with different metal doping: (a) Cu-NPC; (b) Fe-NPC; (c) Mn-NPC; XPS spectra of TM-NPC with different metal doping: Cu 2p (d) and N 1s (g) spectra of Cu-NPC; Fe 2p (e) and N 1s (h) spectra of Fe-NPC; Mn 2p (f) and N 1s (i) spectra of Mn-NPC

图7 Cu-NPC在不同湿度下脱硫性能（a）和吸附量（b）对比

Figure 7 Effect of humidity on the desulfurization performance (a) and adsorption capacity (b) of Cu-NPC

图8 Cu-NPC在不同气源下的脱硫性能（a）和吸附量（b）

Figure 8 Desulfurization performance (a) and adsorption capacity (b) of Cu-NPC using different gas sources

图9 不同温度下Cu-NPC的转化率

Figure 9 The conversion rate of Cu-NPC at different temperatures

图10 Cu-NPC脱硫持久性能

Figure 10 Evaluation of the long-term desulfurization stability of Cu-NPC

图11 Cu-NPC脱硫前后Cu 2p谱图（a）、N 1s谱图（b）；N物种与硫容量相关性分析（c，d）；注:Cu-NPC脱硫后S 2p谱图(e)和in-situ DRIFT谱图(f)

Figure 11 Cu 2p (a) and N 1s (b) spectra for Cu-NPC catalyst before and after desulfurization; Relationships between H2S capacity and N species (c, d); S 2p spectrum (e) and in-situ DRIFT spectra (f) of Cu-NPC after desulfurization

图12 Cu-NPC脱硫机理图

Figure 12 Schematic diagram of the desulfurization mechanism of Cu-NPC

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