Pd nanoparticles on DUT-67-PZDC-derived N-doped carbon for efficient H2 generation from formic acid dehydrogenation

Abstract

It is important to develop heterogeneous catalysts with high efficiency and stability to catalyze formic acid (FA, HCOOH) dehydrogenation. Herein, through pyrolysis of DUT-67-PZDC and etching in a hydrofluoric acid (HF) solution, the HF-etched N-doped carbon (HNDC) carrier was obtained. Palladium nanoparticles (Pd NPs), with an average particle size of 3.0 nm, were prepared on the HNDC support using a simple chemical co-reduction method. The optimized Pd/HNDC catalyst demonstrates excellent catalytic activity, the initial turnover frequency (TOF) value is 6001 h−1 at 50 °C with the incorporation of sodium formate (SF) as an additive, and the FA conversion and hydrogen (H2) selectivity could be up to 100%, which is comparable to the majority of MOF-derived heterogeneous catalysts published to date. Additionally, the Pd/HNDC can maintain good stability in five consecutive FA dehydrogenation runs with only a slight decrease. Such remarkable catalytic performance of Pd/HNDC is mainly ascribed to the unique structure of HNDC support with high surface area and hierarchical pore characteristic, the strong synergistic interaction between Pd NPs and the N sites on HNDC, as well as the ultrasmall size and high dispersion of Pd NPs as the catalytic active site. This work offers an efficient method for assembling highly active catalysts for FA dehydrogenation.