Construction of site-specific magnetic Z-scheme CdS/Fe3O4@N-doped graphene aerogel microtube/N-doped TiO2 with porous structure: enhanced catalytic performance in photo-Fenton reaction.

The development of composite photocatalysts with high charge transfer efficiency, great visible light absorption, and quick recovery has aroused the interest of many researchers. Herein, based on the hydrothermal assisted vacuum freeze drying method, CdS, Fe3O4, and N-TiO2 were, respectively, fixed in the inner, middle, and outer layers of nitrogen-doped graphene aerogel for preparation of the site-specific magnetic porous Z-scheme CdS/Fe3O4@N-doped graphene aerogel microtube/N-doped TiO2 (CdS/Fe3O4@NGAM/N-TiO2) photocatalyst. For the composite, Fe3O4@NGAM carrier with porous and tubular structure not only helps the recycle and reactants/productions mass transport in the photocatalytic process but also ensures the well-steered transfer of electrons and holes from CdS and N-TiO2 in the Z-type heterojunction system, greatly improving the separation of photogenerated carriers. Besides, Fe3O4 can also work as a Fenton catalyst to activate hydrogen peroxide which is generated in situ by CdS. Thus, the CdS/Fe3O4@NGAM/N-TiO2 composite presents excellent degradation efficiencies towards methyl orange ((MO) 98% removal rate within 50 min), bisphenol A ((BPA) 96% removal rate within 50 min), tetracycline hydrochloride ((TCH) 96% removal rate within 120 min) and strong stabilities after 6 cycles. The free radical removal experiments show that ·O2- and ·OH are the main active substances of catalysis, which further confirms the synergistic effect of photocatalysis and Fenton catalysis.

Charge Carriers Localization Effect Revealed through Terahertz Spectroscopy of MXene: Ti3C2Tx.

The transport properties of charge carriers in MXene, a promising material, have been studied using terahertz time-domain spectroscopy (THz-TDS) to examine its potential applications in optical and electronic devices. However, previous studies have been limited by narrow frequency ranges, which have hindered the understanding of the intrinsic mechanisms of carrier transport in MXenes. To address this issue, ultrabroadband THz-TDS with frequencies of up to 15 THz to investigate the complex photoconductances of MXene (Ti3C2Tx) films with different thicknesses are employed. The findings indicate that the electronic localization is substrate-dependent, and this effect decreases with an increase in the number of layers. This is attributed to the screening effect of the high carrier density in Ti3C2Tx. Additionally, the layer-independent photocarrier relaxations revealed by optical pump THz probe spectroscopy (OPTP) provide evidence of the carrier heating-induced screening effect. These results are significant for practical applications in both scientific research and various industries.

Rational synthesis of novel "giant" CuInTeSe/CdS core/shell quantum dots for optoelectronics.

"Giant" core/shell quantum dots (g-QDs) are promising candidates for emerging optoelectronic technologies thanks to their facile structure/composition-tunable optoelectronic properties and outstanding photo-physical/chemical stability. Here, we synthesized a new type of CuInTeSe (CITS)/CdS g-QDs and regulated their optoelectronic properties by controlling the shell thickness. Through increasing the shell thickness, as-prepared g-QDs exhibited tunable red-shifted emission (from 900 to 1200 nm) and prolonged photoluminescence (PL) lifetimes (up to ∼14.0 µs), indicating a formed band structure showing efficient charge separation and transfer, which is further testified by theoretical calculations and ultrafast time-resolved transient absorption (TA) spectroscopy. These CITS/CdS g-QDs with various shell thicknesses can be employed to fabricate photoelectrochemical (PEC) cells, exhibiting improved photoresponse and stability as compared to the bare CITS QD-based devices. The results indicate that the rational design and engineering of g-QDs is very promising for future QD-based optoelectronic technologies.

Long-lived charge separation following pump-wavelength-dependent ultrafast charge transfer in graphene/WS2 heterostructures.

Van der Waals heterostructures consisting of graphene and transition metal dichalcogenides have shown great promise for optoelectronic applications. However, an in-depth understanding of the critical processes for device operation, namely, interfacial charge transfer (CT) and recombination, has so far remained elusive. Here, we investigate these processes in graphene-WS2 heterostructures by complementarily probing the ultrafast terahertz photoconductivity in graphene and the transient absorption dynamics in WS2 following photoexcitation. We observe that separated charges in the heterostructure following CT live extremely long: beyond 1 ns, in contrast to ~1 ps charge separation reported in previous studies. This leads to efficient photogating of graphene. Furthermore, for the CT process across graphene-WS2 interfaces, we find that it occurs via photo-thermionic emission for sub-A-exciton excitations and direct hole transfer from WS2 to the valence band of graphene for above-A-exciton excitations. These findings provide insights to further optimize the performance of optoelectronic devices, in particular photodetection.

Manipulating the Optoelectronic Properties of Quasi-type II CuInS2/CdS Core/Shell Quantum Dots for Photoelectrochemical Cell Applications.

Colloidal core/shell heterostructured quantum dots (QDs) possessing quasi-type II band structure have demonstrated effective surface passivation and prolonged exciton lifetime, leading to enhanced charge separation/transfer efficiencies that are promising for photovoltaic device applications. Herein, we synthesized CuInS2 (CIS)/CdS core/shell heterostructured QDs and manipulated the optoelectronic properties via controlling the CdS shell thickness. The shell-thickness-dependent optical properties indicate the existence of a quasi-type II band structure in such core/shell QDs, which was verified by ultrafast spectroscopy and theoretical simulations. These quasi-type II core/shell QDs having various shell thicknesses are used as light absorbers for the fabrication of solar-driven QDs-based photoelectrochemical (PEC) devices, exhibiting an optimized photocurrent density of ∼6.0 mA/cm2 and excellent stability under simulated AM 1.5G solar illumination. The results demonstrate that quasi-type II CIS/CdS core/shell heterostructured QDs with tailored optoelectronic properties are promising to realize high-performance QDs-based solar energy conversion devices for the production of solar fuels.

A Critical Review on Enhancement of Photocatalytic Hydrogen Production by Molybdenum Disulfide: From Growth to Interfacial Activities.

Ultrathin 2D molybdenum disulfide (MoS2 ), which is the flagship of 2D transition-metal dichalcogenide nanomaterials, has drawn much attention in the last few years. 2D MoS2 has been banked as an alternative to platinum for highly active hydrogen evolution reaction because of its low cost, high surface-to-volume ratio, and abundant active sites. However, when MoS2 is used directly as a photocatalyst, contrary to public expectation, it still performs poorly due to lateral size, high recombination ratio of excitons, and low optical cross section. Besides, simply compositing MoS2 as a cocatalyst with other semiconductors cannot satisfy the practical application, which stimulates the pursual of a comprehensive insight into recent advances in synthesis, properties, and enhanced hydrogen production of MoS2 . Therefore, in this Review, emphasis is given to synthetic methods, phase transitions, tunable optical properties, and interfacial engineering of 2D MoS2 . Abundant ways of band edge tuning, structural modification, and phase transition are addressed, which can generate the neoteric photocatalytic systems. Finally, the main challenges and opportunities with respect to MoS2 being a cocatalyst and coherent light-matter interaction of MoS2 in photocatalytic systems are proposed.

Ultrafast Dynamics of Charge Transfer and Photochemical Reactions in Solar Energy Conversion.

For decades, ultrafast time-resolved spectroscopy has found its way into an increasing number of applications. It has become a vital technique to investigate energy conversion processes and charge transfer dynamics in optoelectronic systems such as solar cells and solar-driven photocatalytic applications. The understanding of charge transfer and photochemical reactions can help optimize and improve the performance of relevant devices with solar energy conversion processes. Here, the fundamental principles of photochemical and photophysical processes in photoinduced reactions, in which the fundamental charge carrier dynamic processes include interfacial electron transfer, singlet excitons, triplet excitons, excitons fission, and recombination, are reviewed. Transient absorption (TA) spectroscopy techniques provide a good understanding of the energy/electron transfer processes. These processes, including excited state generation and interfacial energy/electron transfer, are dominate constituents of solar energy conversion applications, for example, dye-sensitized solar cells and photocatalysis. An outlook for intrinsic electron/energy transfer dynamics via TA spectroscopic characterization is provided, establishing a foundation for the rational design of solar energy conversion devices.

Small molecule-assisted fabrication of black phosphorus quantum dots with a broadband nonlinear optical response.

Ultrathin BP QDs with a uniform size of ∼3.4 nm were prepared via small molecule-assisted liquid phase exfoliation and they exhibited superior broadband nonlinear saturable absorption promising for nonlinear optical applications. Laser photolysis measurement implied that the nonlinear response origin was related to the long-lived electron-hole pairs delocalized within the BP QDs.

Preparation of large size, few-layer black phosphorus nanosheets via phytic acid-assisted liquid exfoliation.

Ultrathin uniform BP nanosheets with lateral dimensions of up to several tens of micrometers were prepared via a small molecule-assisted liquid phase exfoliation method, which exhibited attractive electron accepting abilities from photosensitizers and was thus promising in diverse applications such as photocatalysis and photovoltaics.

Iron-Doped Carbon Nitride-Type Polymers as Homogeneous Organocatalysts for Visible Light-Driven Hydrogen Evolution.

Graphitic carbon nitrides have appeared as a new type of photocatalyst for water splitting, but their broader and more practical applications are oftentimes hindered by the insolubility or difficult dispersion of the material in solvents. We herein prepared novel two-dimensional (2D) carbon nitride-type polymers doped by iron under a mild one-pot method through preorganizing formamide and citric acid precursors into supramolecular structures, which eventually polycondensed into a homogeneous organocatalyst for highly efficient visible light-driven hydrogen evolution with a rate of ∼16.2 mmol g(-1) h(-1) and a quantum efficiency of 0.8%. Laser photolysis and electrochemical impedance spectroscopic measurements suggested that iron-doping enabled strong electron coupling between the metal and the carbon nitride and formed unique electronic structures favoring electron mobilization along the 2D nanomaterial plane, which might facilitate the electron transfer process in the photocatalytic system and lead to efficient H2 evolution. In combination with electrochemical measurements, the electron transfer dynamics during water reduction were depicted, and the earth-abundant Fe-based catalyst may open a sustainable strategy for conversion of sunlight into hydrogen energy and cope with current challenging energy issues worldwide.

A Bioinspired Molecular Polyoxometalate Catalyst with Two Cobalt(II) Oxide Cores for Photocatalytic Water Oxidation.

To overcome the bottleneck of water splitting, the exploration of efficient, selective, and stable water oxidation catalysts (WOCs) is crucial. We report an all-inorganic, oxidatively and hydrolytically stable WOC based on a polyoxometalate [(A-α-SiW9 O34)2Co8(OH)6(H2O)2(CO3)3](16-) (Co8 POM). As a cobalt(II)-based cubane water oxidation catalyst, Co8POM embeds double Co(II)4O3 cores. The self-assembled catalyst is similar to the oxygen evolving complex (OEC) of photosystem II (PS II). Using [Ru(bpy)3](2+) as a photosensitizer and persulfate as a sacrificial electron acceptor, Co8POM exhibits excellent water oxidation activity with a turnover number (TON) of 1436, currently the highest among bioinspired catalysts with a cubical core, and a high initial turnover frequency (TOF). Investigation by several spectroscopy, spectrometry, and other techniques confirm that Co8POM is a stable and efficient catalyst for visible light-driven water oxidation. The results offer a useful insight into the design of water oxidation catalysts.