Dataset of structure-activity relationships in Pd/ZrO2-TiO2 catalysts for furfural reductive amination: Batch vs Operando ATR-FTIR.

Furfural (FUR) is one of the main chemical platforms derived from lignocellulosic biomass and a relevant precursor of value-added compounds such as secondary amines. Among the available synthetic routes, the direct reductive amination of FUR with aniline (ANI) is an attractive and environmentally favourable alternative to displace fossil-based processes. Nevertheless, under hydrogen atmosphere and in the presence of metal-containing catalysts, this transformation is frequently accompanied by parallel pathways, including hydrogenations of the carbonyl group, aromatic rings, and the formation of undesired alcohol derivatives. Therefore, current efforts are focused on the rational design of bifunctional catalysts able to increase the selectivity to the secondary amines while keeping a stable performance. However, there is a lack of readily available and detailed experimental data allowing the elucidation of structure-activity relationships of catalytic systems involving bifunctional mechanisms and under reaction conditions (in operando). This article presents a dataset for the reductive amination of FUR with ANI over Pd/ZrO2-TiO2 catalysts using two reaction systems: (i) traditional batch reactors and (ii) a reactor for in operando measurements via Fourier Transform Infrared Spectroscopy coupled with Attenuated Total Reflectance measurements (FTIR-ATR). The dataset includes catalyst characterization data for several Pd/ZrO2-TiO2 systems in which the Zr/Ti ratio was varied to modulate surface properties (acid density, distribution of Lewis sites, etc.). The applied techniques include N2 physisorption, X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), H2 temperature-programmed reduction (H2-TPR), ammonia temperature-programmed desorption (NH3-TPD), pyridine adsorption infrared spectroscopy (IR-Pyr), transmission electron microscopy (TEM), and Scanning transmission electron microscopy (STEM) coupled with energy-dispersive X-ray spectroscopy (EDX). In addition, the dataset on catalytic activity includes different reaction conditions (solvent media, temperature, pressure, concentration of reactants, intermediates, and N-substrates). Furthermore, reaction profiles acquired by operando FTIR-ATR were integrated with product identification and quantification by gas chromatography-mass spectrometry (GC-MS) and flame ionization (GC-FID). Raw files, processed data, and calculation sheets are provided to facilitate reuse, independent analysis, kinetic treatment, comparative evaluation with related catalytic systems, and data-driven approaches for understanding furfural reductive amination.