Abstract: In one aspect, the disclosure relates to catalytic phase transfer sorbents (PTS) for producing hydrogen-enriched syngas from a carbonaceous feedstock, the PTS comprising a formula selected from ABO3 and An+1BnO3n+1, wherein A comprises one or more alkali metals or alkaline earth metals, wherein B comprises one or more transition metals, and wherein X comprises an anion. Also disclosed is a system for hydrogen generation from carbonaceous feedstocks, the system comprising a gasifier unit for production of H2-rich syngas and a regenerator unit for regeneration of spent PTS. Further disclosed herein is a method for hydrogen generation from carbonaceous feedstocks using the disclosed systems. The disclosed systems can be operated isothermally through 10 or more cycles without degradation in performance, while the disclosed methods can yield 50% or more H2 relative to carbon-containing species. In some aspects, the methods produce little to no CO2.