α-Ni(OH)2表面羟基协同Ni3+位点催化氧化甲醛机理研究

doi:10.15541/jim20230161

无机材料学报 ›› 2023, Vol. 38 ›› Issue (10): 1216-1222.DOI: 10.15541/jim20230161 CSTR: 32189.14.10.15541/jim20230161

所属专题：【能源环境】污染物去除(202312)

α-Ni(OH)₂表面羟基协同Ni³⁺位点催化氧化甲醛机理研究

张瑞阳¹^,²(), 王壹¹^,², 欧博文², 周莹¹^,²()

1.西南石油大学油气藏地质及开发工程全国重点实验室, 成都 610500
2.西南石油大学新能源与材料学院, 成都 610500

收稿日期:2023-04-03 修回日期:2023-05-11 出版日期:2023-10-20 网络出版日期:2023-05-14
通讯作者: 周莹, 教授. E-mail: yzhou@swpu.edu.cn
作者简介:张瑞阳(1990-), 男, 博士. E-mail: ryzhang@swpu.edu.cn
基金资助:
国家自然科学基金(22206159);四川省重大科技专项(2020ZDZX0008)

α-Ni(OH)₂ Surface Hydroxyls Synergize Ni³⁺ Sites for Catalytic Formaldehyde Oxidation

ZHANG Ruiyang¹^,²(), WANG Yi¹^,², OU Bowen², ZHOU Ying¹^,²()

1. National Key Laboratory of Oil and Gas Reservoir Geology and Exploitation, Southwest Petroleum University, Chengdu 610500, China
2. School of New Energy and Materials, Southwest Petroleum University, Chengdu 610500, China

Received:2023-04-03 Revised:2023-05-11 Published:2023-10-20 Online:2023-05-14
Contact: ZHOU Ying, professor. E-mail: yzhou@swpu.edu.cn
About author:ZHANG Ruiyang (1990-), male, PhD. E-mail: ryzhang@swpu.edu.cn
Supported by:
National Natural Science Foundation of China(22206159);Sichuan Science and Technology Program(2020ZDZX0008)

摘要/Abstract

摘要：

室内甲醛污染已成为影响人类生命健康的重要问题之一。以氧气为氧化剂的催化氧化甲醛技术以其条件温和、无毒副产物等优势而受到广泛关注, 但是开发经济高效的催化材料仍然面临巨大的挑战。本工作通过一步水热法制备了α-Ni(OH)₂, 并研究了其催化氧化甲醛机理。测试结果表明, 以水为溶剂、硝酸镍为镍源制备的α-Ni(OH)₂在室温下催化氧化甲醛效率最高, 达到71.2%。原位红外和理论计算分析发现, 由于α-Ni(OH)₂表面丰富的羟基官能团, 吸附的甲醛与α-Ni(OH)₂表面羟基之间存在强烈的相互作用, 增强了对甲醛的活化, 在无氧气条件下实现了甲醛氧化。另一方面, 不同条件处理的α-Ni(OH)₂的XPS分析证实了催化氧化甲醛的活性位点为Ni³⁺, 且氧气可加速Ni³⁺活性位点的回复。α-Ni(OH)₂表面羟基协同活性位点Ni³⁺促进了甲醛的催化氧化, 这与传统氧气解离为速控步的甲醛氧化反应路径明显不同。本研究提出了表面羟基协同活性位点促进甲醛氧化的反应机理, 为催化氧化甲醛技术的实际应用提供了理论基础。

关键词: 催化氧化甲醛, 表面羟基, 反应机理, 反应路径

Abstract:

Indoor formaldehyde (HCHO) pollution has become one of the major issues affecting human health. Catalytic formaldehyde oxidation technology employing oxygen as oxidant has received extensive attention owing to its mild conditions and nontoxic byproducts, but developing affordable and effective catalysts remains a significant hurdle. In this work, α-Ni(OH)₂ was prepared through one-step hydrothermal method and its catalytic formaldehyde oxidation mechanism was investigated. The greatest catalytic formaldehyde elimination rate of 71.2% was demonstrated by α-Ni(OH)₂ at room temperature, which was made with water as the solvent and nickel nitrate as the nickel source. In situ DRIFTS and theoretical calculations revealed that, due to abundant hydroxyl functional groups on the surface of α-Ni(OH)₂, there was strong interaction between adsorbed formaldehyde and hydroxyl group on the surface of α-Ni(OH)₂, which promoted formaldehyde activation and achieved oxidation of formaldehyde without oxygen. On the other hand, the XPS spectra of α-Ni(OH)₂ treated under different conditions confirmed that the active sites of catalytic formaldehyde oxidation were Ni³⁺, and oxygen accelerated the recovery of Ni³⁺ active sites. The surface hydroxyl group of α-Ni(OH)₂ cooperated with the Ni³⁺ active sites achieved excellent catalytic efficiency of formaldehyde oxidation, which was obviously different from the traditional formaldehyde oxidation path with oxygen dissociation as the speed control step. Our work presents a new formaldehyde oxidation pathway controlled by synergy of surface hydroxyl and active sites, and offers a theoretical foundation for the actual use of catalytic formaldehyde oxidation.

Key words: catalytic formaldehyde oxidation, surface hydroxyl, reaction mechanism, reaction path

中图分类号:

TB34

张瑞阳, 王壹, 欧博文, 周莹. α-Ni(OH)₂表面羟基协同Ni³⁺位点催化氧化甲醛机理研究[J]. 无机材料学报, 2023, 38(10): 1216-1222.

ZHANG Ruiyang, WANG Yi, OU Bowen, ZHOU Ying. α-Ni(OH)₂ Surface Hydroxyls Synergize Ni³⁺ Sites for Catalytic Formaldehyde Oxidation[J]. Journal of Inorganic Materials, 2023, 38(10): 1216-1222.

图/表 17

图1 α-Ni(OH)2催化氧化甲醛活性测试

Fig. 1 Catalytic HCHO oxidation over α-Ni(OH)2 (a) Different nickel sources; (b) Different solvents; (c) Different relative humidity; (d) Long time test Mass: 0.1 g; Temperature: 25 ℃; GHSV: 900 h-1; Relative humidity: 60%; Initial concentration of formaldehyde: 2 μL/L

图2 不同溶剂制备α-Ni(OH)2的XRD图谱

Fig. 2 XRD patterns of α-Ni(OH)2 prepared by different solvents

图3 α-Ni(OH)2-water的SEM(a)和TEM(b)照片

Fig. 3 SEM (a) and TEM (b) images of α-Ni(OH)2-water

图4 α-Ni(OH)2-water的XPS图谱

Fig. 4 XPS spectra of α-Ni(OH)2-water (a) C1s; (b) O1s; (c) Ni2p; (d) Ni2p XPS spectra of samples with different treatments

图5 α-Ni(OH)2-water催化氧化甲醛的原位红外光谱图

Fig. 5 In situ DRIFTS of catalytic HCHO oxidation over α-Ni(OH)2-water under different conditions (a) HCHO and N2; (b) HCHO and O2

图6 甲醛在α-Ni(OH)2表面的吸附示意图

Fig. 6 Schematic diagram of HCHO adsorption over α-Ni(OH)2

图7 α-Ni(OH)2催化氧化甲醛示意图

Fig. 7 Schematic diagram of catalytic HCHO oxidation over α-Ni(OH)2

图S1 甲醛净化性能图

Fig. S1 HCHO removal ratio Temperature: 25 ℃; GHSV: 900 h-1; Relative humidity: 60%;Initial concentration of formaldehyde: 2 μL/L

图S2 甲醛净化性能对比图

Fig. S2 Comparison of HCHO removal ratio Temperature: 25 ℃; GHSV: 900 h-1; Relative humidity: 60%; Initial concentration of formaldehyde: 2×10-6

图S3 α-Ni(OH)2-water的吡啶红外光谱

Fig. S3 Pyridine-infrared spectrum of α-Ni(OH)2-water

图S4 不同溶剂制备α-Ni(OH)2的C1s XPS谱图

Fig. S4 C1s XPS spectra of α-Ni(OH)2 prepared by different solvents

图S5 不同溶剂制备α-Ni(OH)2的O1s XPS谱图

Fig. S5 O1s XPS spectra of α-Ni(OH)2 prepared by different solvents

图S6 不同溶剂制备α-Ni(OH)2的Ni2p XPS谱图

Fig. S6 Ni2p XPS spectra of α-Ni(OH)2 prepared by different solvents

图S7 不同溶剂制备α-Ni(OH)2的FT-IR图谱

Fig. S7 FT-IR spectra of α-Ni(OH)2 prepared by different solvents

图S8 不同溶剂制备α-Ni(OH)2的热重分析

Fig. S8 TG curves of α-Ni(OH)2 prepared by different solvents

图S9 α-Ni(OH)2-water和α-Ni(OH)2-PG的N2吸脱附等温线

Fig. S9 N2 adsorption and desorption isotherms of α-Ni(OH)2-water and α-Ni(OH)2-PG

图S10 α-Ni(OH)2-water的EPR测试

Fig. S10 EPR tests of α-Ni(OH)2-water (a) ·O2-; (b) ·OH

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α-Ni(OH)₂表面羟基协同Ni³⁺位点催化氧化甲醛机理研究

α-Ni(OH)₂ Surface Hydroxyls Synergize Ni³⁺ Sites for Catalytic Formaldehyde Oxidation

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