Atomically Dispersed Cobalt/Copper Dual‐Metal Catalysts for Synergistically Boosting Hydrogen Generation from Formic Acid

Abstract

The development of practical materials for (de)hydrogenation reactions is a prerequisite for the launch of a sustainable hydrogen economy. Herein, we present the design and construction of an atomically dispersed dual‐metal site Co/Cu−N−C catalyst allowing significantly improved dehydrogenation of formic acid, which is available from carbon dioxide and green hydrogen. The active catalyst centers consist of specific CoCuN6 moieties with double‐N‐bridged adjacent metal‐N4 clusters decorated on a nitrogen‐doped carbon support. At optimal conditions the dehydrogenation performance of the nanostructured material (mass activity 77.7 L ⋅ gmetal−1 ⋅ h−1) is up to 40 times higher compared to commercial 5 % Pd/C. In situ spectroscopic and kinetic isotope effect experiments indicate that Co/Cu−N−C promoted formic acid dehydrogenation follows the so‐called formate pathway with the C−H dissociation of HCOO* as the rate‐determining step. Theoretical calculations reveal that Cu in the CoCuN6 moiety synergistically contributes to the adsorption of intermediate HCOO* and raises the d‐band center of Co to favor HCOO* activation and thereby lower the reaction energy barrier.

Hydrogen production from chemical hydrogen storage materials over copper‐based catalysts

“…Recently, Li et al designed and prepared atomically dispersed Co/Cu-N-C bimetallic site catalysts by a sacrificial template method and used them for FAD (Figure 10). 405 The active center of the catalyst consists of specific production mass activity of 1300 mL g −1 min −1 under optimal conditions, which far exceeds that of commercial noble metal catalysts such as 5% Pd/C (40 times higher). Moreover, Co/Cu-N-C maintains its high performance over several cycles of reaction and long-term experiments lasting up to 72 h. In situ spectroscopic and kinetic isotope effect experiments confirm that Co/Cu-N-C promotes FAD following the formate pathway and that the C−H bond breaking of HCOO* is the rate-determining step.…”

“…A range of Cu-based catalysts for FAD have been explored by researchers over the years. [391][392][393][394][395][396][397][398][399][400][401][402][403][404][405] "Alloying" is a promising method of enhancing the catalytic efficiency of active metals by combining them with various elements and changing their electronic and geometric states. 406 In 2015, Yamashita et al prepared monodispersed PdCu alloy NPs (Pd 50 Cu 50 /resin 1) in a macroporous basic resin containing the −N(CH 3 ) 2 functional group and applied it to FAD.…”

Asymmetric CoN3P1 single-atom catalytic sites for enhanced transfer hydrodehalogenation

“…24,25 In this regard, Beller's group introduced a standout example, the BMZIF-derived Co–N–C(SACs)-1000, where atomically dispersed cobalt catalysts outperform their nanoparticulate counterparts in FA dehydrogenation (DH) in terms of efficiency, selectivity, and stability. 26 Subsequently, similar cobalt-based SACs have been developed, 27,28 each exhibiting improved efficiency and stability for FA DH. A prominent example in this respect is CoCuN 6 moieties within a nitrogen-doped carbon support (Co/Cu–N–C), which dramatically enhance FA DH performance, up to 40 times higher than commercial 5% Pd/C catalysts.…”

“…A prominent example in this respect is CoCuN 6 moieties within a nitrogen-doped carbon support (Co/Cu–N–C), which dramatically enhance FA DH performance, up to 40 times higher than commercial 5% Pd/C catalysts. 28 Despite these advancements, the majority of cobalt-based SACs are primarily used for FA DH, overlooking their potential to facilitate FA- or formate-driven synthetic processes under mild and eco-friendly conditions.…”

Alkali Metal Ions Stabilizing Copper(I)–Sulfur Bonds for Efficient Formate Production from Electrochemical CO2 Reduction

“…Electrochemical CO 2 reduction reaction (CO 2 RR) is considered as a promising approach to mitigate global warming issues and simultaneously produce value-added chemicals. , Among the wide range of reductive products achieved from CO 2 RR, formic acid (HCOOH) or formate (HCOO – , generally produced in alkaline solutions) has become the research focus due to its wide applications and considerable industrial value . It is also a promising candidate as a liquid hydrogen carrier with the capability of releasing gaseous hydrogen under mild conditions (e.g., at relatively low temperatures of 60–80 °C) . At present, several types of post-transition metal-based electrocatalysts, including Sn-, In-, Pb-, Pd-, and Bi-based electrocatalysts, have been developed for the CO 2 -to-formate conversion with successive progress. − Nevertheless, a large overpotential of up to 1.0 V is generally required to reach the industry-scale current densities (e.g., ≥200 mA cm –2 ), in addition to the pending issues of the insufficient Faradaic efficiency (FE), poor catalyst durability, and environmental toxicity. − …”