ABSTRACT
Photocatalytic solar hydrogen generation, encompassing both overall water splitting and organic reforming, presents a promising avenue for green hydrogen production. This technology holds the potential for reduced capital costs in comparison to competing methods like photovoltaic-electrocatalysis and photoelectrocatalysis, owing to its simplicity and fewer auxiliary components. However, the current solar-to-hydrogen efficiency of photocatalytic solar hydrogen production has predominantly remained low at ≈1-2% or lower, mainly due to curtailed access to the entire solar spectrum, thus impeding practical application of photocatalytic solar hydrogen production. This review offers an integrated, multidisciplinary perspective on photocatalytic solar hydrogen production. Specifically, the review presents the existing approaches in photocatalyst and system designs aimed at significantly boosting the solar-to-hydrogen efficiency, while also considering factors of cost and scalability of each approach. In-depth discussions extending beyond the efficacy of material and system design strategies are particularly vital to identify potential hurdles in translating photocatalysis research to large-scale applications. Ultimately, this review aims to provide understanding and perspective of feasible pathways for commercializing photocatalytic solar hydrogen production technology, considering both engineering and economic standpoints.
ABSTRACT
Photoreforming has been shown to accelerate the H2 evolution rate compared to water splitting due to thermodynamically favorable organic oxidation. In addition, the potential to simultaneously produce solar fuel and value-added chemicals is a significant benefit of photoreforming. To achieve an efficient and economically viable photoreforming process, the selection and design of an appropriate photocatalyst is essential. Carbon nitride is promising as a metal-free photocatalyst with visible light activity, high stability, and low fabrication cost. However, it typically exhibits poor photogenerated charge carrier dynamics, thereby resulting in low photocatalytic performance. Herein, we demonstrate improved carrier dynamics in urea-functionalized carbon nitride with in situ photodeposited Ni cocatalyst (Ni/Urea-CN) for ethanol photoreforming. In the presence of 1 mM Ni2+ precursor, an H2 evolution rate of 760.5 µmol h-1 g-1 and an acetaldehyde production rate of 888.2 µmol h-1 g-1 were obtained for Ni/Urea-CN. The enhanced activity is ascribed to the significantly improved carrier dynamics in Urea-CN. The ability of oxygen moieties in the urea group to attract electrons and to increase the hole mobility via a positive shift in the valence band promotes an improvement in the overall carrier dynamics. In addition, high crystallinity and specific surface area of the Urea-CN contributed to accelerating charge separation and transfer. As a result, the electrons were efficiently transferred from Urea-CN to the Ni cocatalyst for H2 evolution while the holes were consumed during ethanol oxidation. The work demonstrates a means by which carrier dynamics can be tuned by engineering carbon nitride via edge functionalization.
Subject(s)
Nickel , Urea , Ethanol , AcetaldehydeABSTRACT
Photoreforming is a promising alternative to water splitting for H2 generation due to the favorable organic oxidation half-reaction and the potential to simultaneously produce solar fuel and value-added chemicals. Recently, carbon nitride has received significant attention as an inexpensive photocatalyst for the photoreforming process. However, the application of carbon nitride continues to be hampered by its poor photocatalytic performance. Herein, we report for the first time a synergistic modification of an in situ photodeposited Ni cocatalyst on carbon nitride via cyanamide functionalization and solid/liquid interfacial charge-induced activation using excess Ni2+ ions. Synergism between the cyanamide functionalization and charge-induced activation by the excess Ni2+ ions invokes enhanced activity, selectivity, and stability during ethanol photoreforming. A H2 evolution rate of 2.32 mmol h-1 g-1 in conjunction with an acetaldehyde production rate of 2.54 mmol h-1 g-1 was attained for the Ni/NCN-CN. The H2 evolution rate and elevated acetaldehyde selectivity (above 98%) remained consistent under prolonged light illumination. To understand the origin of the complementary promotional effects, the contributions of cyanamide groups and excess Ni2+ ions to selective ethanol photoreforming are decoupled and systematically investigated. The cyanamide functionality on carbon nitride was found to promote hole scavenging for the ethanol oxidation reaction, thereby enabling effective electron transfer to the Ni cocatalyst for H2 evolution. Concomitantly, excess Ni2+ ions remaining in solution created a positively charged environment on the photocatalyst surface, which improved charge carrier utilization and ethanol adsorption. The work highlights the importance of both carbon nitride functionality and charge on the photocatalyst surface in developing a selective photocatalytic reforming system.
