Zhou Chunhui, Zhang Rongmei, Hu Jinsong, Yao Changguang, Liu Zhentao, Duan Aijun, Wang Xilong
Analytical and Testing Center, School of Chemical and Blasting Engineering, Anhui Province Key Laboratory of Specialty Polymers, Anhui Provincial Institute of Modern Coal Processing Technology, Anhui University of Science and Technology, Huainan 232001, China.
Analytical and Testing Center, School of Chemical and Blasting Engineering, Anhui Province Key Laboratory of Specialty Polymers, Anhui Provincial Institute of Modern Coal Processing Technology, Anhui University of Science and Technology, Huainan 232001, China.
J Colloid Interface Sci. 2024 Nov;673:997-1006. doi: 10.1016/j.jcis.2024.06.216. Epub 2024 Jul 9.
The highly dispersed ultrasmall palladium nanoparticles (Pd NPs) (1.7 nm) were successfully immobilized on a N-containing metal-organic framework (MOF, DUT-67-PZDC) using a co-reduction method, and it is used as an excellent catalyst for formic acid dehydrogenation (FAD). The optimized catalyst Pd/DUT-67-PZDC(10, 10 wt% Pd loading) shows 100% hydrogen (H) selectivity and formic acid (FA) conversion at 60 °C, and the commendable initial turnover frequency (TOF) values of 2572 h with the sodium formate (SF) as an additive and 1059 h even without SF, which is better than most reported MOF supported Pd monometallic heterogeneous catalysts. The activation energy (Ea) of FAD is 43.2 KJ/mol, which is lower than most heterogeneous catalysts. In addition, the optimized catalyst Pd/DUT-67-PZDC(10) maintained good stability over five consecutive runs, demonstrating only minimal decline in catalytic activity. The outstanding catalytic performance could be ascribed to the synergistic corporations of the unique structure of DUT-67-PZDC carrier with hierarchical pore characteristic, the metal-support interaction (MSI) between the active Pd NPs and DUT-67-PZDC, the highly dispersed Pd NPs with ultrafine size serve as the catalytic active site, as well as the N sites on the support could act as the proton buffers. This work provides a new paradigm for the efficient H production of FAD by constructing highly active heterogeneous Pd-based catalysts using MOF supports.
通过共还原法成功地将高度分散的超小钯纳米颗粒（Pd NPs）（1.7纳米）固定在含氮金属有机框架（MOF，DUT-67-PZDC）上，并将其用作甲酸脱氢（FAD）的优良催化剂。优化后的催化剂Pd/DUT-67-PZDC（10，钯负载量为10 wt%）在60℃时显示出100%的氢气（H）选择性和甲酸（FA）转化率，以甲酸钠（SF）为添加剂时的初始周转频率（TOF）值为2572 h，即使没有SF时也有1059 h，优于大多数报道的MOF负载的Pd单金属多相催化剂。FAD的活化能（Ea）为43.2 KJ/mol，低于大多数多相催化剂。此外，优化后的催化剂Pd/DUT-67-PZDC（10）在连续五次运行中保持了良好的稳定性，催化活性仅略有下降。优异的催化性能可归因于具有分级孔特征的DUT-67-PZDC载体的独特结构、活性Pd NPs与DUT-67-PZDC之间的金属-载体相互作用（MSI）、作为催化活性位点的高度分散的超细尺寸Pd NPs，以及载体上的N位点可作为质子缓冲剂。这项工作通过使用MOF载体构建高活性的多相Pd基催化剂，为FAD高效制氢提供了新的范例。
