Simultaneously Producing H2 and H2O2 by Photocatalytic Water Splitting: Recent Progress and Future.

The solar-driven overall water splitting (2H2O→2H2 + O2) is considered as one of the most promising strategies for reducing carbon emissions and meeting energy demands. However, due to the sluggish performance and high H2 cost, there is still a big gap for the current photocatalytic systems to meet the requirements for practical sustainable H2 production. Economic feasibility can be attained through simultaneously generating products of greater value than O2, such as hydrogen peroxide (H2O2, 2H2O→H2 + H2O2). Compared with overall water splitting, this approach is more kinetically feasible and generates more high-value products of H2 and H2O2. In several years, there has been an increasing surge in exploring the possibility and substantial progress has been achieved. In this review, a concise overview of the importance and underlying principles of PIWS is first provided. Next, the reported typical photocatalysts for PIWS are discussed, including commonly used semiconductors and cocatalysts, essential design features of these photocatalysts, and connections between their structures and activities, as well as the selected approaches for enhancing their stability. Then, the techniques used to quantify H2O2 and the operando characterization techniques that can be employed to gain a thorough understanding of the reaction mechanisms are summarized. Finally, the current existing challenges and the direction needing improvement are presented. This review aims to provide a thorough summary of the most recent research developments in PIWS and sets the stage for future advancements and discoveries in this emerging area.

Synergistic Effect of Rutile and Brookite TiO2 for Photocatalytic Formic Acid Dehydrogenation.

Solar energy is an ideal clean and inexhaustible energy source. Solar-driven formic acid (FA) dehydrogenation is one of the promising strategies to address safety and cost issues related to the storage, transport, and distribution of hydrogen energy. For FA dehydrogenation, the O-H and C-H cleavages are the key steps, and developing a photocatalyst with the ability to break these two bonds is critical. In this work, both density functional theory (DFT) calculation and experimental results confirmed the positive synergistic effect between brookite and rutile TiO2 for O-H and C-H cleavage in HCOOH. Further, brookite TiO2 is beneficial to the generation of the •OH radical and significantly promotes C-H cleavage in formate. Under optimized conditions, the H2 production efficiency of FA dehydrogenation can reach up to 30.4 µmol·mg-1·h-1, which is the highest value compared with similar reported TiO2-based systems and over 1.7 times the reported highest value of Au0.75Pd0.25/TiO2 photocatalysts. More importantly, after more than 42 days (>500 h) of irradiation, the system still demonstrated high H2 production activity, indicating the potential for practical application. This work provides a valuable strategy to improve both the efficiency and stability of photocatalytic FA dehydrogenation under mild conditions.

The Recent Progress of Oxygen Reduction Electrocatalysts Used at Fuel Cell Level.

Proton exchange membrane fuel cells (PEMFCs) are gaining significant interest as an attractive substitute for traditional fuel cells, with higher energy density, lower environmental pollution, and better operation efficiency. However, the cathode reaction, i.e., the oxygen reduction reaction (ORR), is widely proved to be inefficient, and therefore an obstacle to the widespread development of PEMFCs. The requirement for affordable highly-efficient ORR catalysts is extremely urgent to be met, especially at fuel cell level. Unfortunately, most previous reports focus on the ORR performance at rotating disk electrodes (RDE) level instead of membrane electrode assembly (MEA) level, making it harder to evaluate ORR catalysts operating under real vehicle conditions. Obviously, it is extremely necessary to develop an in-depth understanding of the structure-activity relationship of highly-efficient ORR catalysts applied at MEA level. In this work, an overview of the latest advances in ORR catalysts is provided with an emphasis on their performance at MEA level, hoping to cover the novel and systemic insights for innovative and efficient ORR catalyst design and applications in PEMFCs.

Preparation and characterization of magnetic Fe3O 4/CNT nanoparticles by RPO method to enhance the efficient removal of Cr(VI).

This work described a novel method for the synthesis of high-ferromagnetism nanoparticles (Fe3O4/CNTs) to efficiently remove Cr(VI) from aqueous solution. The Fe3O4/carbon nanotubes (CNTs) were prepared by in situ reduction with post-oxidation method by using cheap and environmentally friendly precursor under mild condition. Magnetic hysteresis loops revealed that Fe3O4/CNTs had superior saturation magnetization (152 emu/g), enabling the highly efficient recovery of Fe3O4/CNTs from aqueous solution by magnetic separation at low magnetic field gradients. FTIR, Raman, XPS, and TEM observations were employed to characterize the physical-chemical properties of Fe3O4/CNTs, demonstrating that CNTs were successfully coated with iron oxide matrix. The adsorption equilibrium of Cr(VI) on Fe3O4/CNTs was reached within 30 min. Langmuir, Freundlich, and Dubinin-Radushkevich isotherm were chosen to analyze the equilibrium data. The results indicated that Langmuir model can well describe the equilibrium data with the maximum adsorption capacity of 47.98 mg/g at room temperature and 83.54 mg/g at 353 K. The adsorption capacity of Fe3O4/CNTs for Cr(VI) was greatly improved as compared to raw CNTs and other similar adsorbents reported. The pseudo-second-order kinetic model provided the best description of Cr(VI) adsorption on Fe3O4/CNTs. Most importantly, possible synthesis mechanism and Cr(VI) removal mechanism were explored. The results suggest that large amounts of Cr(VI) were adsorbed on Fe3O4/CNTs surface by substituting the surface position of -OH and then reducing it to Cr(OH)3 and Cr2O3.