Tailoring Interfaces for Enhanced Methanol Production from Photoelectrochemical CO2 Reduction.

Efficient and stable photoelectrochemical reduction of CO2 into highly reduced liquid fuels remains a formidable challenge, which requires an innovative semiconductor/catalyst interface to tackle. In this study, we introduce a strategy involving the fabrication of a silicon micropillar array structure coated with a superhydrophobic fluorinated carbon layer for the photoelectrochemical conversion of CO2 into methanol. The pillars increase the electrode surface area, improve catalyst loading and adhesion without compromising light absorption, and help confine gaseous intermediates near the catalyst surface. The superhydrophobic coating passivates parasitic side reactions and further enhances local accumulation of reaction intermediates. Upon one-electron reduction of the molecular catalyst, the semiconductor-catalyst interface changes from adaptive to buried junctions, providing a sufficient thermodynamic driving force for CO2 reduction. These structures together create a unique microenvironment for effective reduction of CO2 to methanol, leading to a remarkable Faradaic efficiency reaching 20% together with a partial current density of 3.4 mA cm-2, surpassing the previous record based on planar silicon photoelectrodes by a notable factor of 17. This work demonstrates a new pathway for enhancing photoelectrocatalytic CO2 reduction through meticulous interface and microenvironment tailoring and sets a benchmark for both Faradaic efficiency and current density in solar liquid fuel production.

Aqueous Photoelectrochemical CO2 Reduction to CO and Methanol over a Silicon Photocathode Functionalized with a Cobalt Phthalocyanine Molecular Catalyst.

We report a precious-metal-free molecular catalyst-based photocathode that is active for aqueous CO2 reduction to CO and methanol. The photoelectrode is composed of cobalt phthalocyanine molecules anchored on graphene oxide which is integrated via a (3-aminopropyl)triethoxysilane linker to p-type silicon protected by a thin film of titanium dioxide. The photocathode reduces CO2 to CO with high selectivity at potentials as mild as 0 V versus the reversible hydrogen electrode (vs RHE). Methanol production is observed at an onset potential of -0.36 V vs RHE, and reaches a peak turnover frequency of 0.18 s-1 . To date, this is the only molecular catalyst-based photoelectrode that is active for the six-electron reduction of CO2 to methanol. This work puts forth a strategy for interfacing molecular catalysts to p-type semiconductors and demonstrates state-of-the-art performance for photoelectrochemical CO2 reduction to CO and methanol.