MULTI‐LAYER KESTERITE‐BASED PHOTOCATHODES FOR NH3 PHOTOSYNTHESIS FROM N2 REDUCTION REACTION

The necessity of new methods to substitute the Haber‐Bosch process in the NH3 synthesis, generating fewer greenhouse gases, and dispensing less energy, drove the investigation of the photoelectrocatalytic approach in the N2 reduction reaction (N2RR). For that, this work presents the synthesis and characterization of the layered CZTSSe/CdS/TiO2 photocathode decorated with Pt nanoparticles for application in NH3 production using the photoelectrocatalysis technique. The CZTSSe/CdS/TiO2‐Pt characterization showed a well‐designed and stable photocatalyst synthesized layer by layer with an important contribution of the Pt nanoparticles for the catalyst performance, improving the photocurrent density and the charge transfer. The N2RR in a two‐compartment photochemical cell with 0.1 mol L‐1 Na2SO3 and 0.05 mol L‐1 H2SO4 in the cathodic and anodic chamber, respectively, using CZTSSe/CdS/TiO2‐Pt and under 1 sun of light incidence and applied potential of ‐0.4 VAg/AgCl reached 0.22 mmol L‐1 cm‐2 NH3, a value 28 folds higher than using the catalyst without Pt modification. The superiority of N2RR under the photoelectrocatalysis technique was demonstrated compared to photocatalytic and electrocatalytic techniques, together with the investigation of the supporting electrolyte influence in the cathodic compartment. Additionally, that is the first time a kesterite‐based photocathode has been applied to NH3 photosynthesis, showing excellent photoconversion capability.