Hydrogen (H 2 ), a regenerable and promising energy carrier, acts as an essential role in the construction of a sustainable energy system. Formic acid (HCOOH, FA), a natural biological metabolic products and also accessible through carbon dioxide (CO 2 ) reduction, has a great potential to serve as a prospective H 2 supplier for the fuel cell. Herein, ultrafine and electron-rich IrPdAu alloy nanoparticles with a size of 1.4 nm are highly dispersed on amine-modified mesoporous SiO 2 (NH 2 -SBA-15) and used as a highly active and selective catalyst for fast H 2 production from FA. The as-synthesized IrPdAu/NH 2 -SBA-15 possesses superior catalytic activity and 100% H 2 selectivity with initial turnover frequency values of 6316 h −1 with the additive of sodium formate (SF) and 4737 h −1 even without SF at 298 K, comparable to the most effective heterogeneous catalysts ever published. The excellent performance of IrPdAu/NH 2 -SBA-15 was not only ascribed to the combination of the electronic synergistic effect of trimetallic alloys and the strong metal−support interaction effect but also attributed to the amine (−NH 2 ) alkaline groups grafted on SBA-15, which is beneficial to boost the split of the O−H bond of FA.

Herein, CeO2-modified PdAg alloy nanocomposites were anchored on mesoporous carbon, showing exceedingly high catalytic activity for HCOOH dehydrogenation at room temperature.

PdIr/SBA-15-NH2 nanocomposites were synthesized via a facile surface functionalization and co-reduction method and used as a superior catalyst for complete and fast dehydrogenation of formic acid at room temperature.

Hydrogen (H 2 ) is becoming the most promising candidate for the future sustainable energy systems because it is clean and regenerable. Formic acid (FA, HCOOH), one of the high-value products of the biological metabolic process and the reduction of carbon dioxide (CO 2 ), is considered to be the most efficient hydrogen supplier because it is nontoxic and easy to store and transport and has high hydrogen content. Herein, Pd-ZrO 2 nanoparticles (NPs) immobilized in amine-modified mesoporous silica (Pd-ZrO 2 /SBA-15-NH 2 ) with ultrasmall particle size (1.5 nm) and high dispersion are successfully prepared and applied as an effective catalyst toward the additive-free dehydrogenation of FA at ambient conditions. As a result of the synergistic electronic effects of Pd and ZrO 2 , the strong interaction between the Pd-ZrO 2 NPs and SBA-15-NH 2 substrates and the abundant basic sites originated from ZrO 2 and −NH 2 groups, the as-prepared Pd-ZrO 2 / SBA-15-NH 2 catalyst possesses 100% hydrogen selectivity as well as unexpected catalytic performance with a high turnover frequency value of 1408 h −1 toward CO-free hydrogen production from FA at 298 K, which is even better than most of the effective Pd-based heterogeneous catalysts ever reported. This work offers insights into the facile and controllable synthesis strategy of metal-MO x /support systems for high-efficiency dehydrogenation of chemical hydrides.

Non‐precious‐metal based electrocatalysts with highly‐exposed and well‐dispersed active sites are crucially needed to achieve superior electrocatalytic performance for oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) toward zinc‐air battery (ZAB). Herein, Co‐CoO heterostructures derived from nanosized ZIF‐67 are densely‐exposed and strongly‐immobilized onto N‐doped porous carbon foam (NPCF) through a self‐sacrificial pyrolysis strategy. Benefited from the high exposure of Co‐CoO heterostructures and the favorable mass and electron transfer ability of NPCF, the Co‐CoO/NPCF electrocatalyst exhibits remarkable performance for both ORR (E1/2 = 0.843 V vs RHE) and OER (Ej = 10 mA cm‐2 = 1.586 V vs RHE). Further application of Co‐CoO/NPCF as the air‐cathode in rechargeable ZAB achieves superior performance for liquid‐state ZAB (214.1 mW cm−2 and 600 cycles) and flexible all‐solid‐state ZAB (93.1 mW cm−2 and 140 cycles). Results from DFT calculations demonstrate that the electronic metal‐support interactions between Co‐CoO and NPCF via abundant C‐Nx sites is favorable for electronic structure modulation, accounting for the remarkable performance.