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

doi:10.15541/jim20230161

Abstract

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

CLC Number:

TB34

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.

Figures/Tables 17

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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