Tuning the alloy degree for Pd-M/Al2O3 (M=Co/ Ni /Cu) bimetallic catalysts to enhance the activity and selectivity of dodecahydro-N-ethylcarbazole dehydrogenation

Abstract Hydrogen is a promising candidate to substitute the fossil fuels. However, the efficient hydrogen storage technologies restrict the commercial applications. Developing new catalysts with high activity and selectivity is important for the dehydrogenation reaction in N-ethylcarbazole/dodecahydro-N-ethylcarbazole (NECZ/12H-NECZ) hydrogen storage system. In this work, a series of Pd-M/Al2O3 (M = Co, Ni and Cu) bimetallic catalysts are synthesized successfully and show good performance in the dehydrogenation reaction of 12H-NECZ than the commercial Pd/Al2O3 catalyst. The Pd1Co1/Al2O3 catalyst (Practical Pd content = 2.4136 wt%) showed the highest catalytic performance with 95.34% H2 release amount, TOF of 230.5 min−1 and 85.4% selectivity of NECZ. Combined with the characterization analysis, it can be proposed that the dehydrogenation performance of 12H-NECZ is dependent on the alloy phases, reasonable electronic structures and nanoparticle size of catalysts. The fine-tuned alloy degree and appropriate nanoparticle size of Pd1Co1/Al2O3 bring the 17.7% increase of H2 release amount and 99.5% increase of NECZ selectivity than those of Pd/Al2O3. For the bimetallic catalysts, the enhancement of selectivity of NECZ is mainly from the increase of the kinetic constant of rate-limiting step.