Improved Visible-Light Photocatalytic H₂ Evolution of G-C₃N₄ Nanosheets by Constructing Heterojunctions with Nano-Sized Poly(3-Thiophenecarboxylic Acid) and Coordinating Fe(III)

Abstract

It is highly desirable to enhance the photogenerated charge separation of g-C3N4 by constructing efficient heterojunctions, especially with an additional organic constitution for solar–hydrogen conversion. Herein, g-C3N4 nanosheets have been modified controllably with nano-sized poly(3-thiophenecarboxylic acid) (PTA) through in situ photopolymerization and then coordinated with Fe(III) via the -COOH groups of modified PTA, forming an interface of tightly contacted nanoheterojunctions between the Fe(III)-coordinated PTA and g-C3N4. The resulting ratio-optimized nanoheterojunction displays a ~4.6-fold enhancement of the visible-light photocatalytic H2 evolution activity compared to bare g-C3N4. Based on the surface photovoltage spectra, measurements of the amount of •OH produced, photoluminescence (PL) spectra, photoelectrochemical curves, and single-wavelength photocurrent action spectra, it was confirmed that the improved photoactivity of g-C3N4 is attributed to the significantly promoted charge separation by the transfer of high-energy electrons from the lowest unoccupied molecular orbital (LUMO) of g-C3N4 to the modified PTA via the formed tight interface, dependent on the hydrogen bond interaction between the -COOH of PTA and the -NH2 of g-C3N4, and the continuous transfer to the coordinated Fe(III) with -OH favorable for connection with Pt as the cocatalyst. This study demonstrates a feasible strategy for solar-light-driven energy production over the large family of g-C3N4 heterojunction photocatalysts with exceptional visible-light activities.

Keywords

• graphitic carbon nitride
• poly(3-thiophenecarboxylic acid) modification
• coordinated Fe(III)
• charge transfer and separation
• photocatalytic hydrogen evolution