Zero-valent iron (ZVI) has been confirmed in enhancing methane production by improving interspecies electron transfer during anaerobic digestion (AD) of waste activated sludge (WAS). In this study, we suppose that sulfidated zero-valent iron (S-ZVI), a semiconductor material, has better property of electron transfer in AD process. Based on two-phase anaerobic digestion process, nitrite and S-ZVI were used separately for improving acidogenic phase and methanogenic phase of anaerobic sludge digestion. Based on XRD and XPS, Fe(Ⅱ)-O and Fe(Ⅲ)-O were substituted by Fe(Ⅱ)-S and Fe(Ⅲ)-S after ZVI sulfidation, which increased the electric conductivity of S-ZVI. Nyquist plot and Tafel corrosion curve showed that the sulfidation treatment can reduce impedance of electronic transmission. The results showed that the addition of S-ZVI increased methane production by 24.22% compared with ZVI alone. The addition of S-ZVI increased the relative abundance of Actinobacteria in R3(Raw+S-ZVI) and R6(NO2-+S-ZVI), enhancing the activity of microbial in anaerobic sludge digestion. The relative abundance of Acidobacteriota, Synergistota, WPS-2, Firmicutes, Caldisericota, and Gampylobactenota have changed markedly, and facilitated the activity of acidogenic microbes to produce more biodegradable organic matter, further boosting methane production. The findings of in-situ formation of S-ZVI in R5 anaerobic digestion saves the economic cost of S-ZVI preparation, which will be helpful for the extensive application of this technology.
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