Ultrafast electron transfer at the In2O3/Nb2O5 S-scheme interface for CO2 photoreduction.

Constructing S-scheme heterojunctions proves proficient in achieving the spatial separation of potent photogenerated charge carriers for their participation in photoreactions. Nonetheless, the restricted contact areas between two phases within S-scheme heterostructures lead to inefficient interfacial charge transport, resulting in low photocatalytic efficiency from a kinetic perspective. Here, In2O3/Nb2O5 S-scheme heterojunctions are fabricated through a straightforward one-step electrospinning technique, enabling intimate contact between the two phases and thereby fostering ultrafast interfacial electron transfer (<10 ps), as analyzed via femtosecond transient absorption spectroscopy. As a result, powerful photo-electrons and holes accumulate in the Nb2O5 conduction band and In2O3 valence band, respectively, exhibiting extended long lifetimes and facilitating their involvement in subsequent photoreactions. Combined with the efficient chemisorption and activation of stable CO2 on the Nb2O5, the resulting In2O3/Nb2O5 hybrid nanofibers demonstrate improved photocatalytic performance for CO2 conversion.

Plasmonic Near-Infrared-Response S-Scheme ZnO/CuInS2 Photocatalyst for H2O2 Production Coupled with Glycerin Oxidation.

Solar fuel synthesis is intriguing because solar energy is abundant and this method compensates for its intermittency. However, most photocatalysts can only absorb UV-to-visible light, while near-infrared (NIR) light remains unexploited. Surprisingly, the charge transfer between ZnO and CuInS2 quantum dots (QDs) can transform a NIR-inactive ZnO into a NIR-active composite. This strong response is attributed to the increased concentration of free charge carriers in the p-type semiconductor at the interface after the charge migration between ZnO and CuInS2, enhancing the localized surface plasmon resonance (LSPR) effect and the NIR response of CuInS2. As a paradigm, this ZnO/CuInS2 heterojunction is used for H2O2 production coupled with glycerin oxidation and demonstrates supreme performance, corroborating the importance of NIR response and efficient charge transfer. Mechanistic studies through contact potential difference (CPD), Hall effect test, and finite element method (FEM) calculation allow for the direct correlation between the NIR response and charge transfer. This approach bypasses the general light response issues, thereby stepping forward to the ambitious goal of harnessing the entire solar spectrum.

Enhanced Solar Fuel Production over In2 O3 @Co2 VO4 Hierarchical Nanofibers with S-Scheme Charge Separation Mechanism.

The conversion of CO2 into valuable solar fuels via photocatalysis is a promising strategy for addressing energy shortages and environmental crises. Here, novel In2 O3 @Co2 VO4 hierarchical heterostructures are fabricated by in situ growing Co2 VO4 nanorods onto In2 O3 nanofibers. First-principle calculations and X-ray photoelectron spectroscopy (XPS) measurements reveal the electron transfer between In2 O3 and Co2 VO4 driven by the difference in work functions, thus creating an interfacial electric field and bending the bands at the interfaces. In this case, the photogenerated electrons in In2 O3 transport to Co2 VO4 and recombine with its holes, indicating the formation of In2 O3 @Co2 VO4 S-scheme heterojunctions and resulting in effective separation of charge carriers, as confirmed by in situ irradiation XPS. The unique S-scheme mechanism, along with the enhanced optical absorption and the lower Gibbs free energy change for the production of * CHO, significantly contributes to the efficient CO2 photoreduction into CO and CH4 in the absence of any molecule cocatalyst or scavenger. Density functional theory simulation and in situ diffuse reflectance infrared Fourier transform spectroscopy are employed to elucidate the reaction mechanism in detail.

Soil horizons regulate bacterial community structure and functions in Dabie Mountain of the East China.

Soil bacterial communities regulate nutrient cycling and plant growth in forests. Although these bacterial communities vary with soil nutrients and plant traits, the variation and degree with soil horizons in different forest types remain unclear. Here, bacterial communities of 44 soil samples from organic horizon (O horizon) and mineral horizon (M horizon) of three forest types (Cunninghamia, broad-leaved and Pinus forests) in subtropical forests of Dabie Mountain, China were analyzed based on amplicon sequencing. We assessed the effects of soil horizons and forest types on bacterial communities. The results showed that the bacterial richness and diversity were significantly higher in the O horizon than in the M horizon. Furthermore, the bacterial community composition and functions were also remarkably different between the two soil horizons. Furthermore, forest types could affect bacterial community composition but not for diversity and functions. Moreover, soil organic matter, including the total organic carbon, available phosphorus, total organic nitrogen, available potassium, ammonium nitrogen, and pH were main drivers for bacterial community composition. The results propose robust evidence that soil horizons strongly driven bacterial community composition and diversity, and suggest that microhabitat of soil bacterial communities is important to maintain the stability of forest ecosystem.

Designing reliable and accurate isotope-tracer experiments for CO2 photoreduction.

The photoreduction of carbon dioxide (CO2) into renewable synthetic fuels is an attractive approach for generating alternative energy feedstocks that may compete with and eventually displace fossil fuels. However, it is challenging to accurately trace the products of CO2 photoreduction on account of the poor conversion efficiency of these reactions and the imperceptible introduced carbon contamination. Isotope-tracing experiments have been used to solve this problem, but they frequently yield false-positive results because of improper experimental execution and, in some cases, insufficient rigor. Thus, it is imperative that accurate and effective strategies for evaluating various potential products of CO2 photoreduction are developed for the field. Herein, we experimentally demonstrate that the contemporary approach toward isotope-tracing experiments in CO2 photoreduction is not necessarily rigorous. Several examples of where pitfalls and misunderstandings arise, consequently making isotope product traceability difficult, are demonstrated. Further, we develop and describe standard guidelines for isotope-tracing experiments in CO2 photoreduction reactions and then verify the procedure using some reported photoreduction systems.

Sustained CO2-photoreduction activity and high selectivity over Mn, C-codoped ZnO core-triple shell hollow spheres.

Solar conversion of CO2 into energy-rich products is one of the sustainable solutions to lessen the global energy shortage and environmental crisis. Pitifully, it is still challenging to attain reliable and affordable CO2 conversion. Herein, we demonstrate a facile one-pot approach to design core-triple shell Mn, C-codoped ZnO hollow spheres as efficient photocatalysts for CO2 reduction. The Mn ions, with switchable valence states, function as "ionized cocatalyst" to promote the CO2 adsorption and light harvesting of the system. Besides, they can capture photogenerated electrons from the conduction band of ZnO and provide the electrons for CO2 reduction. This process is continuous due to the switchable valence states of Mn ions. Benefiting from such unique features, the prepared photocatalysts demonstrated fairly good CO2 conversion performance. This work is endeavoured to shed light on the role of ionized cocatalyst towards sustainable energy production.

Graphdiyne-modified TiO2 nanofibers with osteoinductive and enhanced photocatalytic antibacterial activities to prevent implant infection.

Titanium implants have been widely used in bone tissue engineering for decades. However, orthopedic implant-associated infections increase the risk of implant failure and even lead to amputation in severe cases. Although TiO2 has photocatalytic activity to produce reactive oxygen species (ROS), the recombination of generated electrons and holes limits its antibacterial ability. Here, we describe a graphdiyne (GDY) composite TiO2 nanofiber that combats implant infections through enhanced photocatalysis and prolonged antibacterial ability. In addition, GDY-modified TiO2 nanofibers exert superior biocompatibility and osteoinductive abilities for cell adhesion and differentiation, thus contributing to the bone tissue regeneration process in drug-resistant bacteria-induced implant infection.

Unique S-scheme heterojunctions in self-assembled TiO2/CsPbBr3 hybrids for CO2 photoreduction.

Exploring photocatalysts to promote CO2 photoreduction into solar fuels is of great significance. We develop TiO2/perovskite (CsPbBr3) S-scheme heterojunctions synthesized by a facile electrostatic-driven self-assembling approach. Density functional theory calculation combined with experimental studies proves the electron transfer from CsPbBr3 quantum dots (QDs) to TiO2, resulting in the construction of internal electric field (IEF) directing from CsPbBr3 to TiO2 upon hybridization. The IEF drives the photoexcited electrons in TiO2 to CsPbBr3 upon light irradiation as revealed by in-situ X-ray photoelectron spectroscopy analysis, suggesting the formation of an S-scheme heterojunction in the TiO2/CsPbBr3 nanohybrids which greatly promotes the separation of electron-hole pairs to foster efficient CO2 photoreduction. The hybrid nanofibers unveil a higher CO2-reduction rate (9.02 µmol g-1 h-1) comparing with pristine TiO2 nanofibers (4.68 µmol g-1 h-1). Isotope (13CO2) tracer results confirm that the reduction products originate from CO2 source.

Photocatalytic CO2 reduction of C/ZnO nanofibers enhanced by an Ni-NiS cocatalyst.

The photocatalytic reduction of CO2 into valuable hydrocarbon fuels via solar energy is a promising strategy for carbon utilization. In the present paper, a hierarchical Ni-NiS/C/ZnO photocatalyst was prepared via the in situ photodeposition of compact Ni-NiS nanosheets onto C/ZnO electrospun nanofibers. The existence of metallic Ni and NiS was confirmed by X-ray photoelectron spectroscopy. Photoluminescence (PL) and time-resolved PL spectra revealed that the cocatalyst Ni-NiS enhanced the charge separation efficiency of the C/ZnO nanofibers. The as-prepared Ni-NiS/C/ZnO showed enhanced CO2 reduction activity, with CO and CH4 production rates 10 and 15 times greater than those of pristine C/ZnO under 350 W visible light illumination. The intermediates of CH3O-, HCHO, and HCOO- were detected by in situ Fourier transform infrared spectroscopy, confirming that CO2 reduction is a complex reaction with multiple steps. The 13C isotopic tracer method proved that CH4 and CO were obtained from the reduction of CO2 rather than from other carbon species in the environment. The amorphous carbon in C/ZnO could promote optical absorption, improve conductivity and reduce the interfacial charge transport resistance. Ni-NiS improved the electron-hole-pair separation of the C/ZnO nanofibers. The observed enhancement in photocatalytic activity was largely attributed to higher light utilization and effective electron-hole separation. This work proves that Ni-NiS is a promising cocatalyst to ZnO for photocatalytic CO2 reduction.

In Situ Grown Monolayer N-Doped Graphene on CdS Hollow Spheres with Seamless Contact for Photocatalytic CO2 Reduction.

Photocatalytic CO2 reduction is an effective way to simultaneously mitigate the greenhouse effect and the energy crisis. Herein, CdS hollow spheres, on which monolayer nitrogen-doped graphene is in situ grown by chemical vapor deposition, are applied for realizing effective photocatalytic CO2 reduction. The constructed photocatalyst possesses a hollow interior for strengthening light absorption, a thin shell for shortening the electron migration distance, tight adhesion for facilitating separation and transfer of carriers, and a monolayer nitrogen-doped graphene surface for adsorbing and activating CO2 molecules. Achieving seamless contact between a photocatalyst and a cocatalyst, which provides a pollution-free and large-area transport interface for carriers, is an effective strategy for improving the photocatalytic CO2 reduction performance. Therefore, the yield of CO and CH4 , as dominating products, can be increased by four and five times than that of pristine CdS hollow spheres, respectively. This work emphasizes the importance of contact interface regulation between the photocatalyst and the cocatalyst and provides new ideas for the seamless and large-area contact of heterojunctions.