Realization of a photoelectrochemical cascade for the generation of methanol, a liquid solar fuel

Biochemical networks use reaction cascades to selectively reduce CO2 using energy from sunlight, but can similar selectivity be achieved by applying a cascade approach to an engineered system? Here, we report the design and implementation of a two-step photoelectrochemical (PEC) cascade to a liquid solar fuel: reduction of CO2 to CO and subsequent reduction of CO to methanol. The potentials required to perform the reductions were generated using custom-made III-V-based three-terminal tandem (3TT) solar cells. Cobalt phthalocyanine immobilized on multi-walled carbon nanotubes (CoPc/MWCNT) catalyzed both reactions. Multiphysics simulations of electrolyte flow and non-illuminated electrochemical measurements were used to narrow the operating parameters for the CoPc/MWCNT 3TT photocathodes. The champion integrated photocathode produced methanol with 3.8 ± 0.4% Faradaic efficiency (FE), with tested photocathodes having 0.7-3.8% methanol FE. Products were quantified by nuclear magnetic resonance spectroscopy and gas chromatography. The current output of the tested photocathodes was highly stable, and methanol production continued over multiple experiments. The low methanol yield is attributed to insufficient CO flux to, and CO2 depletion at, the methanol-producing subcell when both contacts are active, which is supported by the observation that a control photoelectrode slightly outperformed the methanol production of the 3TT device. Methanol production ceased when the 3TT subcell driving CO reduction was deactivated, supporting the assignment of a cascade mechanism. The major factors resulting in low methanol FE by the CoPc/MWCNT 3TT photocathodes are insufficient CO2 depletion at the methanol-producing contact and uncertainty in operating potential selection using the 3TT design. Although the CoPc/MWCNT 3TT photocathode is not yet highly selective, this work develops the basic science principles underlying the PEC cascade, demonstrates the co-design of a 3TT-based photoelectrode to produce carbon-based fuels, and finally discusses routes for improving product yields with this concept, including CO2 supply optimization and alternative photoelectrode and catalyst materials.