Transition Metal Ion Doping on ZIF-8 Enhances the Electrochemical CO2 Reduction Reaction.

The electrochemical reduction of CO2  to diverse value-added chemicals is a unique, environmentally friendly approach for curbing greenhouse gas emissions while addressing sluggish catalytic activity and low Faradaic efficiency (FE) of electrocatalysts. Here, zeolite-imidazolate-frameworks-8 (ZIF-8) containing various transition metal ions-Ni, Fe, and Cu-at varying concentrations upon doping are fabricated for the electrocatalytic CO2 reduction reaction (CO2 RR) to carbon monoxide (CO) without further processing. Atom coordination environments and theoretical electrocatalytic performance are scrutinized via X-ray absorption spectroscopy (XAS) and density functional theory (DFT) calculations. Upon optimized Cu doping on ZIF-8, Cu0.5 Zn0.5 /ZIF-8 achieves a high partial current density of 11.57 mA cm-2 and maximum FE for CO of 88.5% at -1.0 V (versus RHE) with a stable catalytic activity over 6 h. Furthermore, the electron-rich sp2 C atom facilitates COOH* promotion after Cu doping of ZIF-8, leading to a local effect between the zinc-nitrogen (Zn-N4 ) and copper-nitrogen (Cu-N4 ) moieties. Additionally, the advanced CO2 RR pathway is illustrated from various perspectives, including the pre-H-covered state under the CO2 RR. The findings expand the pool of efficient metal-organic framework (MOF)-based CO2 RR catalysts, deeming them viable alternatives to conventional catalysts.

Effects of Propylene Oxide End Capping on Amination of Polyalkylene Glycols.

Polyalkylene glycols with two different end-capping groups of ethylene oxide (EO) and propylene oxide (PO) were used for amination to produce polyetheramine (PEA) on cobalt-based catalysts. Although it is known that the amination of secondary alcohol is more difficult than that of primary alcohol, PO end-capped block copolymers showed remarkably enhanced activity toward PEA and selectivity toward the primary amine compared to EO end-capped block copolymers.

Improved H2 utilization by Pd doping in cobalt catalysts for reductive amination of polypropylene glycol.

Cobalt based catalysts having enhanced H2 dissociation and desorption were synthesized by inserting a trace amount of palladium. These catalysts were used for the reductive amination of polypropylene glycol (PPG) to polyetheramine (PEA). The catalytic activity toward PEA was significantly increased by incorporating an extremely low content of palladium (around 0.01 wt%) into cobalt based catalysts. The Pd inserted cobalt catalysts promoted reduction of cobalt oxide to cobalt metal and inhibited formation of cobalt nitride in the reductive amination. The Pd inserted cobalt catalysts not only enhanced hydrogen dissociation but also accelerated hydrogen desorption by increasing the electron density of cobalt through interaction between cobalt and palladium. These play a critical role in reducing cobalt oxide or cobalt nitride to cobalt metal as an active site for the reductive amination. Thus, the Pd inserted cobalt catalysts provide improved catalytic performance toward PEA production by maintaining the cobalt metal state.