**Experimental and Computational Evaluation of Heavy Metal Cation Adsorption for Molecular Design of Hydrothermal Char**

**Louise Delahaye 1,**†**, John Thomas Hobson 1,**†**, Matthew Peter Rando 1, Brenna Sweeney 1, Avery Bernard Brown 1, Geo**ff**rey Allen Tompsett 1, Ayten Ates 2, N. Aaron Deskins <sup>1</sup> and Michael Thomas Timko 1,\***


Received: 16 July 2020; Accepted: 10 August 2020; Published: 14 August 2020

**Abstract:** A model hydrochar was synthesized from glucose at 180 ◦C and its Cu(II) sorption capacity was studied experimentally and computationally as an example of molecular-level adsorbent design. The sorption capacity of the glucose hydrochar was less than detection limits (3 mg g<sup>−</sup>1) and increased significantly with simple alkali treatments with hydroxide and carbonate salts of K and Na. Sorption capacity depended on the salt used for alkali treatment, with hydroxides leading to greater improvement than carbonates and K<sup>+</sup> more than Na+. Subsequent zeta potential and infrared spectroscopy analysis implicated the importance of electrostatic interactions in Cu(II) sorption to the hydrochar surface. Computational modeling using Density Functional Theory (DFT) rationalized the binding as electrostatic interactions with carboxylate groups; similarly, DFT calculations were consistent with the finding that K<sup>+</sup> was more effective than Na<sup>+</sup> at activating the hydrochar. Based on this finding, custom-synthesized hydrochars were synthesized from glucose-acrylic acid and glucose-vinyl sulfonic acid precursors, with subsequent improvements in Cu(II) adsorption capacity. The performance of these hydrochars was compared with ion exchange resins, with the finding that Cu(II)-binding site stoichiometry is superior in the hydrochars compared with the resins, offering potential for future improvements in hydrochar design.

**Keywords:** hydrochar; alkali treatment; copper ions; adsorption; computational
