Mechanisms for Cr(VI) reduction by alcohols over clay edges: Reactive differences between ethanol and ethanediol, and selective conversions to Cr(IV), Cr(III) and Cr(II) species.

Abstract Catalytic reduction by alcohols over clay minerals works efficiently under a wide range of pH and represents an emerging approach to control Cr(VI) contamination. Herein, mechanisms for Cr(VI) adsorption and reduction at clay edges are addressed by dispersion-corrected periodic DFT calculations, considering different active sites, and types (monohydric and polyhydric) and coverage of alcohols. Cr(VI) adsorbs favorably at clay edges, forming direct bonds and strong H-bonds. Mechanisms for Cr(VI) reduction by alcohols are largely determined by π-conjugation development, and efficient conversion conduces to Cr(VI) removal. Cr(II), Cr(III) and Cr(IV) are useful for different purposes, and high selectivity towards these products is realized through rational catalysts design: 1) Cr(IV) dominates at Al3+ site with all ethanol coverage, Al3+ site with high-coverage ethanediol, and Mg2+ site with low-coverage ethanol; 2) Cr(III) dominates at Al3+ and Mg2+ sites with low-coverage ethanediol; 3) Cr(II) dominates at Mg2+ site with high-coverage ethanol or ethanediol. Results agree finely with experimental observations available, and significant new insights have been provided for Cr management and recycling. Detailed electronic structure and vibrational analyses, which can also guide future experimental studies, manifest that Cr(VI) reduction progresses are effectively monitored by ESR and FT-IR techniques.