RESUMEN
The development of high-activity photocatalysts is crucial for the current large-scale development of photocatalytic hydrogen applications. Herein, we have developed a strategy to significantly enhance the hydrogen photocatalytic activity of Cu/Pr di-atom co-modified TiO2 architectures by selectively anchoring Cu single atoms on the oxygen vacancies of the TiO2 surface and replacing a trace of Ti atoms in the bulk with rare earth Pr atoms. Calculation results demonstrated that the synergistic effect between Cu single atoms and Pr atoms regulates the electronic structure of Cu/Pr-TiO2, thus promoting the separation of photogenerated carriers and their directional migration to Cu single atoms for the photocatalytic reaction. Furthermore, the d-band center of Cu/Pr-TiO2, which is located at -4.70 eV, optimizes the adsorption and desorption behavior of H*. Compared to TiO2, Pr-TiO2, and Cu/TiO2, Cu/Pr-TiO2 displays the best H* adsorption Gibbs free energy (-0.047 eV). Furthermore, experimental results confirmed that the photogenerated carrier lifetime of Cu/Pr-TiO2 is not only the longest (2.45 ns), but its hydrogen production rate (34.90 mmol g-1 h-1) also significantly surpasses those of Cu/TiO2 (13.39 mmol g-1 h-1) and Pr-TiO2 (0.89 mmol g-1 h-1). These findings open up a novel atomic perspective for the development of optimal hydrogen activity in dual-atom-modified TiO2 photocatalysts.
RESUMEN
Photocatalytic water splitting for clean hydrogen production has been a very attractive research field for decades. However, the insightful understanding of the actual active sites and their impact on catalytic performance is still ambiguous. Herein, a Pr-doped TiO2-supported Cu single atom (SA) photocatalyst is successfully synthesized (noted as Cu/Pr-TiO2). It is found that Pr dopants passivate the formation of oxygen vacancies, promoting the density of photogenerated electrons on the CuSAs, and optimizing the electronic structure and H* adsorption behavior on the CuSA active sites. The photocatalytic hydrogen evolution rate of the obtained Cu/Pr-TiO2 catalyst reaches 32.88 mmol g-1 h-1, 2.3 times higher than the Cu/TiO2. Innovatively, the excellent catalytic activity and performance is attributed to the active sites change from O atoms to CuSAs after Pr doping is found. This work provides new insight for understanding the accurate roles of single atoms in photocatalytic water splitting.
RESUMEN
Potassium-ion batteries (PIBs) have attracted much attention due to their low production cost and abundant resources. Germanium is a promising alloying-type anode with a high theoretical capacity for PIBs, yet suffering significant volume expansion and sluggish potassium-ion transport kinetics. Herein, a rational strategy is formulated to disperse Ge atoms into transition metal V-S sulfide frameworks to form a loosely packed and metallic GeV4 S8 medium. The theoretical prediction shows that GeV4 S8 is conducive to the adsorption and diffusion of K+ . The V-S frameworks provide fast ion/electron diffusion channels and also help to buffer the volume expansion during K+ insertion. In situ and ex situ characterizations manifest that KGe alloy clusters are constrained and dispersed by potassiated VS2 topological structure during discharging, and revert to the original GeV4 S8 after charging. Consequently, as a novel anode for PIBs, GeV4 S8 provides a high specific capacity of ≈400 mAh g-1 at 0.5 C, maintaining 160 mAh g-1 even at 12.5 C and ≈80% capacity after 1000 cycles at 5 C, superior to most of the state-of-the-art anode materials. The proposed strategy of combining alloy and intercalation dual-functional units is expected to open up a new way for high-capacity and high-rate anode for PIBs.
RESUMEN
Liquid metals (LMs) are emerging as new functional materials with rather unique physical or chemical behaviors. They are generally safe and nontoxic, have high boiling points, reflectivities, good thermal and electrical conductivities, flexibility, fluidity, self-healing capability and remain in liquid state at room temperature. However, the further applications of LMs are limited by their single-color physical appearance, such as working in the situations with imposed stringent requirements for color and aesthetics. Recently, the color and fluorescence functionalization of LMs have overcome many conventional technical bottlenecks and opened significant potential for emerging applications in numerous fields owing to their rich colors and unique liquid structure. In this review, the recent developments in the optical properties, color and fluorescence effects of LMs are comprehensively investigated. The synthesis, structures, properties, chromogenic mechanisms, and potential photoelectric applications of colorful LMs are systematically analyzed and compared. The effectiveness and characteristics of colorful LMs induced by coating, mixing, compounding, surface modification, external stimuli are provided, aiming to establish a potential system for the synthesis and practices of colorful LMs. Finally, the challenges and prospects in the field have also been identified and explained to preferably guide further scientific and technical research in the coming time.
