Mesoporous Silica Supported Pd-MnOx Catalysts with Excellent Catalytic Activity in Room-Temperature Formic Acid Decomposition.

Min-Ho Jin,Sung-Wook Lee,Duckkyu Oh,Jong-Soo Park,Ju-Hyoung Park,Kwan-Young Lee,Chun-Boo Lee,Dong-Wook Lee

doi:10.1038/srep33502

Min-Ho Jin, Sung-Wook Lee + Show 6 more

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https://doi.org/10.1038/srep33502

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Abstract

For the application of formic acid as a liquid organic hydrogen carrier, development of efficient catalysts for dehydrogenation of formic acid is a challenging topic, and most studies have so far focused on the composition of metals and supports, the size effect of metal nanoparticles, and surface chemistry of supports. Another influential factor is highly desired to overcome the current limitation of heterogeneous catalysis for formic acid decomposition. Here, we first investigated the effect of support pore structure on formic acid decomposition performance at room temperature by using mesoporous silica materials with different pore structures such as KIE-6, MCM-41, and SBA-15, and achieved the excellent catalytic activity (TOF: 593 h−1) by only controlling the pore structure of mesoporous silica supports. In addition, we demonstrated that 3D interconnected pore structure of mesoporous silica supports is more favorable to the mass transfer than 2D cylindrical mesopore structure, and the better mass transfer provides higher catalytic activity in formic acid decomposition. If the pore morphology of catalytic supports such as 3D wormhole or 2D cylinder is identical, large pore size combined with high pore volume is a crucial factor to achieve high catalytic performance.

Highlights

For the application of formic acid as a LOHC for an energy source for fuel cells, the dehydrogenation of formic acid is highly desired, and the catalytic selectivity for dehydrogenation and dehydration depends on the catalytic surface, temperature, pH value in reaction system, formic acid concentration and so on ref
We used mesoporous silica KIE-6 as a catalytic support for formic acid decomposition, because the pore properties of KIE-6 such as pore size, pore volume, and surface area can be readily controlled by changing the concentration of glycerol template and silica nanoparticle size
Compared KIE6-b with KIE-6-c, it was revealed that the increase in glycerol concentration of glycerol-silica nanosphere (G-SN) nanocomposites led to the increase in pore size and pore volume of KIE-6 with surface area maintained (Table S2)

Summary

Introduction

For the application of formic acid as a LOHC for an energy source for fuel cells, the dehydrogenation of formic acid is highly desired, and the catalytic selectivity for dehydrogenation and dehydration depends on the catalytic surface, temperature, pH value in reaction system, formic acid concentration and so on ref. Mori et al.[34] investigated FA decomposition of Pd and Pd-Ag nanoparticles within a basic resin with N(CH3)[2] functional groups They demonstrated that the weak basicity of resin and the small particle size of Pd are important factors in achieving good performances for formic acid decomposition at room-temperature. Pd/MSC-30 catalyst showed a highly efficient and complete hydrogen generation in a formic acid-sodium formate system, providing TOF value as high as 750 h−1 at room-temperature. In case of using additives such as sodium formate, the catalytic activity for heterogeneous catalysts was comparable to that for the most active homogeneous catalysts. The Pd-MnOx catalysts supports on NH2-functionalized KIE-6 showed the excellent catalytic activity (TOF: 540.6 h−1) for additive-free formic acid decomposition at room temperature[38]

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