Lewis acid-oxygen vacancy interfacial synergistic catalysis over SO42−/Ce0.84Zr0.16O2–WO3–ZrO2 for N,N-diethylation of aniline with ethanol

Herein, a new mechanism involving Lewis acid-oxygen vacancy interfacial synergistic catalysis for aniline N,N-diethylation with ethanol was proposed, and the SO₄²⁻/Ce_0.84Zr_0.16O₂–WO₃–ZrO₂ catalyst (SCWZ) with both Lewis acid sites and oxygen vacancies was synthesized by the hydrothermal method, which shows better catalytic activity than the reported solid acidic catalysts. Besides, the SO₄²⁻/ZrO₂ (SZ) and SO₄²⁻/WO₃–ZrO₂ (SWZ) catalysts were also prepared and compared with SCWZ to investigate the synergistic effect of each component. The SO₄²⁻ and WO₃ mainly generate Lewis acid by bonding with ZrO₂, which is beneficial for the fracture of the N–H bond in aniline. The Ce_0.84Zr_0.16O₂ solid solution mainly plays a vital role in generating the oxygen vacancies as the interface active species, which can participate in stripping –OH from ethanol, then the carbocation will also be released, which only needs 1.3805 kcal/mol energy, calculated by density functional theory (DFT), to be input. In comparison, the traditional reaction mechanism needs the Brønsted acidic sites to promote the protonation of ethanol, then dehydration and subsequent formation of carbocation followed, and 108.6846 kcal/mol energy needs to be input, which is far higher than that of the new mechanism. The apparent activation energy (E_a) over SCWZ was measured by experiment to be 34.09 kJ/mol, which is much lower than that of SWZ (47.10 kJ/mol) and SZ (54.37 kJ/mol), illustrating comparatively preferable kinetics for SCWZ than that of SWZ and SZ. Besides, the conversion of aniline and selectivity to N,N-diethylaniline over SCWZ reach almost 100% and 73%, respectively. The SCWZ can be renewed for 4 times without rapid deactivation, and the longevity of SCWZ is longer than that of SWZ and SZ, as the loaded SO₄²⁻ and tetragonal ZrO₂ are stabilized by Ce_0.84Zr_0.16O₂ and WO₃, respectively.     

Analysis and optimization of high temperature proton exchange membrane (HT-PEM) fuel cell based on surrogate model

The stoichiometric ratio and flow channel geometry play a vital role in the performance of high temperature proton exchange membrane (HT-PEM) fuel cells. Because of the high cost of experiments or simulations, most analyses and optimization of the stoichiometric ratio and flow channel geometry are limited to several points in the entire design domain. In this study, an analysis and optimization method for HT-PEM fuel cells based on the surrogate model was proposed. Surrogate models were constructed using some of the available budgets of samples to analyze and optimize the entire design domain. With this method, it was indicated that the effect of the cathode stoichiometric ratio is more significant to the cell performance than the anode stoichiometric ratio and there are significant nonlinear interactions among the flow channel geometry parameters. At the fixed operating voltage, the flow channel geometry with the maximum current density and that with the maximum real power were obtained. Compared with the base design, the designs obtained by the surrogate model improve the current density and real power by 10.54% and 3.93%, respectively. Thus, this analysis and optimization method is demonstrated to be helpful and deserves attention in future research.