Novel Amorphous Carbons for the Adsorption of Phosphate: Part I. Elucidation of Chemical Structure of N-Metal-Doped Chars

Michael Ayiania; Aidan Garcia; Sohrab Haghighi Mood; Jean-Sabin McEwen; Manuel Garcia-Perez

doi:10.1021/acsomega.1c05718

Novel Amorphous Carbons for the Adsorption of Phosphate: Part I. Elucidation of Chemical Structure of N-Metal-Doped Chars

ACS Omega. 2022 Apr 22;7(17):14490-14504. doi: 10.1021/acsomega.1c05718. eCollection 2022 May 3.

Authors

Michael Ayiania¹, Aidan Garcia², Sohrab Haghighi Mood¹, Jean-Sabin McEwen^{1

2

3

4

5}, Manuel Garcia-Perez¹

Affiliations

¹ Department of Biological Systems Engineering, Washington State University, Pullman, Washington 99164, United States.
² Gene and Linda Voiland School of Chemical Engineering and Bioengineering, Pullman, Washington 99164, United States.
³ Department of Physics and Astronomy, Washington State University, Pullman, Washington 99164, United States.
⁴ Department of Chemistry, Washington State University, Pullman, Washington 99164, United States.
⁵ Institute for Integrated Catalysis, Pacific Northwest National Laboratory, Richland, Washington 99352, United States.

Abstract

Due to phosphate's necessity in agriculture and its danger to the environment, the development of adsorbents for its removal has been the subject of intensive research activity. Although the introduction of nitrogen functionality to chars and modification of biochar with metals have proven to change the character of the char structure, making it more active toward nutrients, there is no study regarding the doping of biochar with metals and nitrogen simultaneously for the adsorption of phosphates. This paper is the first of two in which we report the production, characterization, and evaluation of N-metal-doped biochars from cellulose for phosphate removal from liquid effluents. In this part, we describe the production and characterization of N-Ca-, N-Fe-, and N-Mg-doped biochars. The elemental composition and surface area of each of the materials produced is reported. Elemental and surface characterization of the chars are reported with the largest N content appearing at a temperature of 800 °C (12.5 wt %) and a maximum surface area for biochar produced at 900 °C (1314 m²/g). All of the adsorbents were visualized by scanning electron microscope (SEM), confirming that although there are some crystals on the surface of the biochar produced, most of the N, Mg, and Ca are part of the polyaromatic ring structure. Transmission electron microscope (TEM) images clearly show the formation of nanoclusters with the metals in the case of N-Fe and N-Ca biochars. The N-Mg biochars show a uniform distribution of the Mg through the carbon surface. X-ray photoelectron spectroscopy (XPS) studies of the biochars produced with metals and varying nitrogen levels clearly show Mg and Ca peaks shifting their position in the presence of N, suggesting the formation of stable structures between metals and N in the carbon polyaromatic ring system. To elucidate the nature of these structures, we conducted DFT-based calculations on different configurations of the nitrogenated structures. The calculated binding energy shifts were found to closely match the XPS experimental binding energy, confirming the likelihood of these structures in biochar. Finally, based on our experimental and modeling results, we hypothesize that an important fraction of the Mg and Ca is introduced to these biochars at the edges. Another fraction of Mg and Ca is in the form of phthalocyanine-like internal structures. More experimental studies are needed to confirm the formation of these very interesting structures and their potential use as adsorbents or catalysts.