Peroxymonosulfate activation based on Co9S8@N−C: A new strategy for highly efficient hydrogen production and synchronous formaldehyde removal in wastewater

doi:10.1016/j.jmst.2022.05.023

Abstract

Abstract:

Formaldehyde (FA), as an important chemical raw material, has been widely used in many fields. However, the discharge of a large amount of FA-containing wastewater poses a serious threat to the environment and human health. Recently, the in-situ hydrogen energy release technology of hydrogen-containing stable liquid has been extensively explored due to its safe storage. Exploring a robust method to achieve FA removal and synchronous in-situ hydrogen release from FA containing wastewater is of great significant for environmental protection and energy crisis alleviation. Here, we have innovatively introduced peroxymonosulfate (PMS) activation technology into FA removal and hydrogen production simultaneously. The composite of nitrogen doped carbon coating Co₉S₈ nanotubes (Co₉S₈@N−C) is employed as a proof of concept for FA decomposition and simultaneously hydrogen production based on PMS activation system. As expected, the Co₉S₈@N−C/PMS system presents much superior hydrogen production efficiency and satisfactory FA removal rate towards FA wastewater than those of common catalysis, photocatalysis and Fenton reaction in the basic condition in a wide range of FA concentration. The hydrogen yield reaches a value as high as 471 μmol within 60 min, corresponding to a FA degradation rate of 30% with an initial FA concentration of 0.722 mol L⁻¹. Characterizations and density functional theory (DFT) calculations suggest that the free radical process dominated by superoxide radical (O₂⋅⁻) and nonradical process dominated by singlet oxygen (¹O₂), which are induced by Co₉S₈@N−C/PMS system, are responsible for highly efficient hydrogen production via FA degradation. These generated O₂⋅⁻and ¹O₂ can extract ⋅H from FA to form ⋅OOH intermediate, which can further combine with the ⋅H from water to produce hydrogen. This study provides an applicable technique for environmental purification and new energy development based on FA containing wastewater.

Key words: Peroxymonosulfate activation, Co₉S₈@N-C, Hydrogen evolution, Formaldehyde removal

Caiyan Gao, Xuezhen Feng, Lian Yi, Xiaoyong Wu, Renji Zheng, Gaoke Zhang, Yubiao Li. Peroxymonosulfate activation based on Co₉S₈@N−C: A new strategy for highly efficient hydrogen production and synchronous formaldehyde removal in wastewater[J]. J. Mater. Sci. Technol., 2022, 127: 256-267.

Figures/Tables 9

Fig. 1. (a) Schematic diagram for the preparation of Co9S8@N?C. (b) SEM, (c) TEM and, (d) HRTEM images of Co9S8@N?C. (e) XRD patterns of Co9S8@N?C, N?C and, Co9S8. (f) N2 adsorption-desorption isotherms (the inset: pore size distribution curves) and (g) Raman spectra of Co9S8@N?C and Co9S8. XPS spectra of Co9S8@N?C: (h) Co 2p, (i) C 1s and (j) N 1s.

Fig. 2. (a) Hydrogen evolution in dehydrogenation of FA and (b) corresponding FA degradation efficiency over Co9S8@N?C/PMS system; NaOH concentration = 0.6 mol L?1; FA concentration= mol L?1; T = 25 °C. (c) Hydrogen evolution of different reaction systems in dehydrogenation of FA and (d) hydrogen evolution of different catalysts in FA dehydrogenation over Co9S8@N?C/PMS system; NaOH concentration = 0.6 mol L?1; FA concentration = 0.722 mol L?1; PMS = 0.3 g L?1; Cata. = 0.2 g L?1; T = 25 °C.

Fig. 3. (a) Hydrogen evolution from a FA solution with different FA concentrations over Co9S8@N?C/PMS system and (b) corresponding FA removal efficiency. (c) Hydrogen production and (d) FA removal performances of Co9S8@N?C/PMS system in different water systems (Han River, Yangtza River and Donghu Lake) with a concentration of 0.722 mol L?1. NaOH concentration = 0.6 mol L?1; Cata. = 0.5 g L?1; PMS = 0.4 g L?1; T = 25 °C.

Fig. 4. Hydrogen evolution from FA solution over Co9S8@N?C/PMS system with (a) different dosage of Co9S8@N?C, (b) PMS, and (c) NaOH. (d) Effect of temperature on hydrogen evolution from a FA solution over Co9S8@N?C/PMS system. NaOH concentration = 0.6 mol L?1; HCHO concentration = 0.722 mol L?1; PMS = 0.3 g L?1; Cata. = 0.2 g L?1; T = 25 °C.

Fig. 5. (a) Effect of (a) Cl?, (b) NO3? and (c) HCO3? on H2 evolution from a HCHO solution over Co9S8@N?C/PMS system; NaOH concentration = 0.6 mol L?1; Cata. = 0.2 g L?1; PMS = 0.3 g L?1; T = 25 °C.

Fig. 6. (a) Reusability test of Co9S8@N?C for hydrogen evolution. (b) Co 2p spectra of fresh and used Co9S8@N?C.

Fig. 7. (a) Hydrogen evolution from FA and methanol solution; FA/methanol concentration = 0.722 mol L?1; NaOH concentration = 0.6 mol L?1; Cata. = 0.5 g L?1; PMS = 0.4 g L?1; T = 25 °C. (b) FA degradation efficiency with and without methanol: FA concentration = 0.003 mol L?1 (The highest concentration of methanol-free FA solution available in the market is 0.003 mol L?1); NaOH concentration = 0.6 mol L?1; T = 25 °C; Cata. = 0.5 g L?1; PMS = 0.4 g L?1. (c) Hydrogen evolution from FA solution and (d) corresponding FA degradation efficiency in different atmospheres, FA concentration = 0.722 mol L?1; NaOH concentration = 0.6 mol L?1; Cata. = 0.5 g L?1; PMS = 0.4 g L?1; T = 25 °C.

Fig. 8. (a) Polarization curves with scan rate of 5 mV s?1, (b) cyclic voltammetry (CV) curves with scan rate of 50 mV s?1, (c) Nyquist plots, and (d) I-t curves of Co9S8@N?C and Co9S8. The structure of PMS absorbed on (e) Co9S8(1)/PMS and (g) Co9S8(1)N?C/PMS. The charge difference distribution of (f) Co9S8(1)@N?C/PMS and (h) Co9S8(1)@N?C/PMS.

Fig. 9. (a) Hydrogen evolution from FA degradation of Co9S8@N?C/PMS system with respect to various scavengers. The identification of different reactive oxidizing species recorded by using (b) DMPO (water serves as solvent), (c) TEMP, and (d) DMPO (methanol serves as solvent).

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Peroxymonosulfate activation based on Co₉S₈@N−C: A new strategy for highly efficient hydrogen production and synchronous formaldehyde removal in wastewater

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