Effect of citric acid modification on the properties of hydrochar and pyrochar and their adsorption performance toward methylene blue: crucial roles of minerals and oxygen functional groups.

Modification is widely used to enhance the adsorption performance of pristine hydrochar (HBC) and pyrochar (BC). However, comparisons between modified HBC and BC toward pollutant removal have rarely been reported. In this study, pristine HBC and BC derived from rice straw were first produced, and then citric acid (CA) was used as a modifier to synthesize CA-modified HBC (CAHBC) and CA-modified BC (CABC). Furthermore, the adsorption performance of biochars toward methylene blue (MB) was investigated. The results showed that BC exhibits relatively rough surfaces and contains more minerals (ash), whereas HBC has plentiful O-containing functional groups and fewer minerals. CA modification partially removed minerals from the surface of BC, which weakened the ion exchange, surface complexation, and n-π interaction, resulting in a lower adsorption ability toward MB. By contrast, CA produced more O-containing functional groups on the surface of HBC, which strengthened the hydrogen bonding and electrostatic interaction, thus increasing the adsorption capacity toward MB. The two-compartment model showed a good fit to the adsorption process of MB on CAHBC, and the isotherm data for MB adsorption by HBC and CAHBC are suitable for the Freundlich model. The highest adsorption amount of MB using CAHBC was 80.13 mg·g, which was 27.66% higher than that for CABC. Fourier transform infrared spectroscopy and X-ray photoelectron spectroscopy analysis indicated that the carboxyl groups in the surface functional groups of CAHBC played a crucial role in the MB adsorption process. In addition, CAHBC showed a good performance for a wide range of pH values (4.0-10.0) and under the interference of coexisting ions, and also presented a recycling ability. Furthermore, the adsorption of MB on CAHBC biochar was a spontaneous, exothermic, degree-of-randomness-increasing process. Consequently, CA modification of HBC is a promising strategy and could be used for MB removal from aquatic environments.