Research Projects

The transition to a hydrogen (H₂)-based economy is a pivotal component of India’s strategy to achieve net-zero carbon emissions; however, its large-scale deployment is hindered by critical challenges associated with its production, storage, and transportation. Liquid organic hydrogen carriers (LOHCs) such as formic acid (FA) offer a compelling solution as they can be produced from sustainable biomass oxidation and carbon dioxide (CO₂) reduction processes. FA is a stable, non-toxic, and readily transportable compound that can decompose to generate H₂ and CO₂ under mild conditions. Currently, most FA dehydrogenation studies are carried out in batch reactors using aqueous FA and expensive promoters. Additionally, the catalysts are largely based on noble metals like Pt, Pd, and Ag, which show high reactivity but are expensive and impractical for large-scale use. Cu-based catalysts, while significantly more economical, suffer from rapid deactivation, limiting their utility in long-duration processes. Our central hypothesis is that rationally designed Cu@X core–shell catalysts supported on oxides can enable stable and selective low-temperature FA-H₂O mixture dehydrogenation in a flow reactor, while also exhibiting activity toward electrochemical CO₂ reduction to FA, thereby offering a dual-function catalytic system for H₂ and carbon integration. This project aims to develop a new class of cost-effective, Cu-based core–shell alloy catalysts (Cu@X; X = Pd and Ni; Cu = core; secondary metal = shell) supported on functional oxide supports (TiO₂, ZnO, CeO₂) to overcome the activity and stability limitations. The oxide supports are anticipated to play a synergistic role by tuning the electronic properties of the metal core–shell structure and providing additional catalytic functionalities, including proton transfer mediation through surface hydroxyl groups. This study focuses on gas-phase FA dehydrogenation under continuous flow, which is more representative of real-world applications compared to conventional aqueous-phase, batch systems. Furthermore, water vapor in the gas stream is hypothesized to facilitate proton transfer during FA decomposition, mimicking the beneficial effects observed in aqueous systems. Additionally, the beneficial effects of water (H₂O) will enable us to use dilute FA-H₂O mixtures that are produced from biomass oxidation processes directly in H₂ production systems. Scientific objectives and experiments of the project are: 1. Design and synthesis of core–shell Cu@X nanoparticles supported on oxide carriers using reproducible methods 2. Evaluation of catalytic performance in a continuous-flow reactor operating below 400 K to assess H₂ production, selectivity, and long-term stability with and without water vapor 3. Mechanistic studies using apparent activation energy measurements, reaction kinetics, and in situ infrared/Raman spectroscopy to elucidate structure–activity relationships and identify active sites 4. Exploration of electrochemical CO₂ reduction using the same catalysts, targeting FA as the reduction product, to establish a closed-loop system for CO₂ capture and utilization. This work addresses multiple challenges in H₂ energy and carbon management by creating an integrated catalyst platform capable of both H₂ release from FA and CO₂ utilization. The project will: • Deliver stable and low-cost catalysts for continuous, low-temperature H₂ generation • Provide fundamental insights into Cu-alloy catalysis, advancing our understanding of how metal–metal and metal–support interactions govern FA decomposition • Enable the development of sustainable LOHC systems that are compatible with real-world flow systems, moving beyond laboratory-scale batch processes • Contribute to carbon-neutral fuel cycles, where CO₂ released during FA dehydrogenation is electrochemically converted back into FA.