Thorium(IV) adsorption onto multilayered Ti₃C₂T_x MXene: a batch, X-ray diffraction and EXAFS combined study

The interlayer regulation of layered environmental adsorption materials such as two-dimensional early transition metal carbides and carbonitrides (MXenes) plays an important role in their purification performance for specific pollutants. Here the enhanced uptake of Th^IV by multilayered titanium carbides (Ti₃C₂T_x) through a hydrated intercalation strategy is reported. Th^IV adsorption behaviors of three Ti₃C₂T_x samples with different c lattice parameters were studied as a function of contact time, pH, initial concentration, temperature and ion strength in batch experiments. The results indicated that the Th^IV uptake was pH and ionic strength dependent, and the adsorption process followed the pseudo-second-order kinetics and the heterogeneous isotherm (Freundlich) model. Thermodynamic data suggested that the adsorption process of all MXene samples was a spontaneous endothermic reaction. The dimethyl sulfoxide intercalated hydrated Ti₃C₂T_x featured the largest interlayer space and exhibited the highest Th^IV adsorption capacity (162 mg g^-1 at pH 3.4 or 112 mg g^-1 at pH 3.0), reflecting the significant increase in available adsorption sites from Ti₃C₂T_x interlayers. The adsorption mechanism has been clarified based on adsorption experiments and spectroscopic characterizations. An ion exchange process was proposed for the interaction between hydrated MXenes and Th^IV, where H⁺ from surface [Ti-O]^-H⁺ groups were the primary active sites on Ti₃C₂T_x. Extended X-ray absorption fine structure (EXAFS) fitting results, in combination with X-ray diffraction (XRD) and Fourier transform infrared spectroscopy (FTIR) analyses, clearly indicated that Th^IV mainly formed the outer-sphere complexes on Ti₃C₂T_x surface through electrostatic interaction under strong acid conditions, while at pH > 3.0 the adsorption mechanism was determined by inner-sphere coordination and electrostatic interaction together.