A Simple and Effective Principle for a Rational Design of Heterogeneous Catalysts for Dehydrogenation of Formic Acid

Abstract

Efficient and selective dehydrogenation of formic acid is a key challenge for a fuel‐cell‐based hydrogen economy. Though the development of heterogeneous catalysts has received much progress, their catalytic activity remains insufficient. Moreover, the design principle of such catalysts are still unclear. Here, experimental and theoretical studies on a series of mono‐/bi‐metallic nanoparticles supported on a NH2‐N‐rGO substrate are combined for formic acid dehydrogenation where the surface energy of a metal is taken as a relevant indicator for the adsorption ability of the catalyst for guiding catalyst design. The AuPd/NH2‐N‐rGO catalyst shows record catalytic activity by reducing the energy barrier of rate controlling steps of formate adsorption and hydrogen desorption. The obtained excellent results both in experiments and simulations could be extended to other important systems, providing a general guideline to design more efficient catalysts.

Ultrafine PdAu nanoparticles immobilized on amine functionalized carbon black toward fast dehydrogenation of formic acid at room temperature

“…Obviously, the signicant enhancement of the catalytic performance of Pd 0.6 Au 0.4 /VXC-72-NH 2 could be ascribed to the hydrophilic VXC-72-NH 2 support for the synthesis of ultrane PdAu NPs. The catalytic activity is much higher than that of Pd or Pd-based alloy supported by amine functionalized rGO, 21,24,26,27,37 mesoporous carbon, 25 MOFs, 29,35 and mesoporous silica, [32][33][34]36 as listed in Table 1. As reported in the literature, 15 for supported noble metal catalysts, the interaction between the metal and support is closely related to the catalytic activity.…”

“…18,19 The dehydration pathway is an undesired side reaction and should be strictly controlled because CO is highly toxic and capable of poisoning Pt-based fuel cell catalysts. In recent years, many heterogeneous catalysts have been developed for FA dehydrogenation, [20][21][22][23][24][25][26][27][28][29][30][31][32][33][34][35][36][37] and among them amine functionalized graphene, MOFs and mesoporous silica are generally used to support gold (Au), palladium (Pd) and Pdbased alloy NPs. Depending on the nature of support materials and preparation methods, some catalysts exhibited efficient dehydrogenation activities.…”

“…Depending on the nature of support materials and preparation methods, some catalysts exhibited efficient dehydrogenation activities. For instance, Jiang and coworkers prepared AuPd NPs supported on amine functionalized graphene, and the catalyst gave a TOF value of 4445.6 h À1 at 298 K. 27 Masuda et al reported PdAg NPs supported on mesoporous carbon functionalized with p-phenylenediamine, which exhibited a high TOF of 5638 h À1 at 348 K. 25 Xu and coworkers prepared highly dispersed palladium nanoclusters immobilized on a nitrogen (N)-functionalized porous carbon support with a TOF of 8414 h À1 at 333 K. 10 Compared with graphene, MOFs, mesoporous silica, mesoporous carbon, active carbons and carbon black are industrialscale produced and cost-effective supports, which have widely been used as the support of noble metals for many industrial catalysts. Herein, we report a facile and efficient approach to synthesize well-dispersed PdAu NPs immobilized on amine functionalized carbon black (VXC-72).…”

Anchoring Pd-nanoparticles on dithiocarbamate- functionalized SBA-15 for hydrogen generation from formic acid

“…Despite the homogeneous catalysts based on Ir, Ru, and Fe organometallic complex usually have great catalytic activity and selectivity, while gold 25 , Platinum 26 , and palladium 4 well known heterogeneous catalysts used in the decomposition of FA. However, some reports have shown that nanostructure with base Pd such as Au 0.5 Pd 0.5 /NH 2 -N-rGO 27 , Pd-MIL-125 28 , Pd 1 Au 1 /30-LA 29 , AP-SiO 2 @PDA-NGO@Pd 30 , PdAu-MnOx/N-SiO 2 31 , CrAuPd/N-SiO 2 32 , IrPdAu/NH 2 -SBA-15 33 , Ag 0.2 Au 0.4 Pd 0.4 /rGO 34 , Au@Pd/UiO-66(Zr x Ti y ) 35 , Au–Pd/MIL-101 36 , and PdCoNi/TiO 2 37 , can efficiently decomposed FA under neat condition. Recently, our research group explored the catalytic application of Pd@Cu-MOF 38 and Pd@Cr-MOF 39 with open metal sites as an ideal Pd-catalyst for H 2 generation from FA in neat condition.…”

Palladium Supported on Porous Chitosan–Graphene Oxide Aerogels as Highly Efficient Catalysts for Hydrogen Generation from Formate

“…The main reasons for this preference is the non-gaseous physical state of formic acid and its derivatives, and their wide availability via the catalytic hydrogenation of CO 2 . A large number of studies describe various catalysts for formic acid and formate decomposition into hydrogen and CO 2 [5]. Most of the catalysts for formate decomposition are transition metals having well established hydrogenating/dehydrogenating activity [6].…”