Study of Non-Noble-Metal-Based Metal–Nitrogen–Carbon Catalysts for Formic Acid Dehydrogenation

Abstract

Formic acid (FA) is a safe, renewable, and promising hydrogen carrier. A critical challenge is the effective screening of the suitable non-noble-metal-based catalysts for FA dehydrogenation to substitute expensive noble-metal-based ones. Here, a study of all possible catalysts with M–N–C structures (M = 12 metals, −N–C = nitrogen-doped graphene-like surface) for FA dehydrogenation has been conducted using density functional theory (DFT) and followed by experimental analysis. Based on the adsorption energy of critical intermediates, preliminary screening suggests Co as a possible active metal for M–N–C. Experiment and further DFT calculations suggest that atomically dispersed Co sites (Co–N1–C3, Co–N2–C2, and Co–N3–C) are preferable for FA dehydrogenation. The appropriate N contents are critical to the catalytic activity, whose amount can be tuned by choosing different sacrifice templates and the pyrolysis temperature.

Second Sphere Effects Promote Formic Acid Dehydrogenation by a Single‐Atom Gold Catalyst Supported on Amino‐Substituted Graphdiyne

“…The TOF values are 6.2 × 10 2 , 1.4 × 10 3 , 3.0 × 10 3 , 6.6 × 10 3 h À 1 at 313, 323, 333, and 343 K, respectively (Figure S13). As shown in Figure S14, the TOF value of 6.6 × 10 3 h À 1 for Au/ GDYÀ NH 2 at 343 K is significantly higher than those of other SACs on carbon nanomaterials [19] (720 h À 1 for Pd SAC on N-doped carbon at 398 K; [19e] 800 h À 1 for Pt SAC on Ndoped carbon nanofibers at 398 K [19d] ) and most of the gold nanoparticles catalysts [6b, 15f, 20] while lower than some of Aubased bimetallic or trimetallic catalysts. [15e, 21] The apparent activation energy (E a ) estimated from the Arrhenius plot (Figure 3b and Figure S13) for FA dehydrogenation catalyzed by Au/GDYÀ NH 2 was 71.61 kJ mol À 1 , which is slightly smaller than that of Au/GDY (E a = 72.13 kJ mol À 1 ) while almost the same as those of the most active homogeneous catalysts.…”

Atomically Dispersed Co on N-Doped Porous Carbon for the Highly Efficient Catalytic Oxidation of Aromatic Alcohols to Acids and Nitriles

“…With the increase in the temperature, g-C 3 N 4 , functioning as a sacrificial template, transformed into a N-doped carbon matrix and confined Co atoms to porous carbon nanosheets, which were derived from glucose during pyrolysis. Notably, g-C 3 N 4 prevented the aggregation of Co atoms, thus facilitating the production of atomically dispersed active Co sites . Finally, a material comprising a porous structure and abundant N atoms was formed; these characteristics assisted in the stability of the Co species and contributed to the production of single Co atoms that were anchored to the N-doped carbon matrix.…”

“…Notably, g-C 3 N 4 prevented the aggregation of Co atoms, thus facilitating the production of atomically dispersed active Co sites. 27 Finally, a material comprising a porous structure and abundant N atoms was formed; these characteristics assisted in the stability of the Co species and contributed to the production of single Co atoms that were anchored to the Ndoped carbon matrix. A detailed experimental procedure for the preparation of Co/NC SACs is given in the Supporting Information.…”

Active site imprinting on Ti oxocluster metal–organic frameworks for photocatalytic hydrogen release from formic acid

“…[5] Catalytic FA decomposition at room temperature has been reported using noble metals, [6][7][8][9][10] making the process of low applicability. Other transition metals can also promote hydrogen release from FA, [11][12][13][14][15] but they require some heating, occur at slower rate and are much less efficient. In addition, due to the known dissolution of metals in acid medium and the ability of FA to form soluble metal-coordination complexes, corrosion of the catalyst and/or metal leaching are some of the limitations generally encountered in such a process.…”