Selective Methylation of Amines with Carbon Dioxide and H2

Owing to the increasing emissions of carbon dioxide (CO(2)), human life and the ecological environment have been affected by global warming and climate changes. To mitigate the concentration of CO(2) in the atmosphere various strategies have been implemented such as separation, storage, and utilization of CO(2). Although it has been explored for many years, hydrogenation reaction, an important representative among chemical conversions of CO(2), offers challenging opportunities for sustainable development in energy and the environment. Indeed, the hydrogenation of CO(2) not only reduces the increasing CO(2) buildup but also produces fuels and chemicals. In this critical review we discuss recent developments in this area, with emphases on catalytic reactivity, reactor innovation, and reaction mechanism. We also provide an overview regarding the challenges and opportunities for future research in the field (319 references).

Green plants convert CO(2) to sugar for energy storage via photosynthesis. We report a novel catalyst that uses CO(2) and hydrogen to store energy in formic acid. Using a homogeneous iridium catalyst with a proton-responsive ligand, we show the first reversible and recyclable hydrogen storage system that operates under mild conditions using CO(2), formate and formic acid. This system is energy-efficient and green because it operates near ambient conditions, uses water as a solvent, produces high-pressure CO-free hydrogen, and uses pH to control hydrogen production or consumption. The extraordinary and switchable catalytic activity is attributed to the multifunctional ligand, which acts as a proton-relay and strong π-donor, and is rationalized by theoretical and experimental studies.