Synchrotron Radiation Based X-ray Absorption Spectroscopy: Fundamentals and Applications in Photocatalysis.

Photocatalysis is one of the most promising green technologies to utilize solar energy for clean energy achievement and environmental governance. There is a knotty problem to rational designing high-performance photocatalyst, which largely depends on an in-depth insight into their structure-activity relationships and complex photocatalytic reaction mechanisms. Synchrotron radiation based X-ray absorption spectroscopy (XAS) is an important characterization method for photocatlayst to offer the element-specific key geometric and electronic structural information at the atomic level, on this basis, time-resolved XAS technique has a huge impact on mechanistic understanding of photochemical reaction owing to their powerful ability to probe, in real-time, the electronic and geometric structures evolution within photocatalysis reactions. This review will focus on the fundamentals of XAS and their applications in photocatalysis. The detailed applications obtained from XAS is described through the following aspects: 1) identifying local structure of photocatalyst; 2) uncovering in situ structure and chemical state evolution during photocatalysis; 3) revealing the photoexcited process. We will provide an in depth understanding on how the XAS method can guide the rational design of highly efficient photocatalyst. Finally, a systematic summary of XAS and related significance is made and the research perspectives are suggested.

Surface plasma modification of cellulose acetate fiber filter for the adsorption of typical components in smoke components.

Surface modification of cellulose acetate filter rods with low temperature plasma was performed to explore the retention and adsorption effect of modified filter rods on typical components (CO, H2O, benzene, and formaldehyde) in cigarette smoke. The surface structure and composition of the cellulose acetate filter rods were modified by changing the plasma treatment time. The modified filter rods were characterized by N2 physical adsorption (BET), scanning electron microscopy (SEM), X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), contact angle of H2O, Fourier transform infrared spectroscopy (FTIR) and in situ DRIFTS. Various functional groups were found on the surface of filter rods with the introduction of plasma modification, which exhibited strong retention performance for water vapor in cigarette smoke at room temperature and significantly enhanced adsorption for harmful substances (CO, benzene, and formaldehyde) in cigarette smoke.

Facet-Dependent Photocatalytic Behavior of Rutile TiO2 for the Degradation of Volatile Organic Compounds: In Situ Diffuse Reflectance Infrared Fourier Transform Spectroscopy and Density Functional Theory Investigations.

In this study, a custom rutile titanium dioxide (TiO2) photocatalyst with a single exposed surface was utilized to investigate the facet-dependent photocatalytic mechanism of toluene. The degradation of toluene was dynamically monitored using diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS) technology coupled with theoretical calculations. The findings demonstrated that the photocatalytic degradation rate on the TiO2 (001) surface was nearly double that observed on the TiO2 (110) surface. This remarkable enhancement can be attributed to the heightened stability in the adsorption of toluene molecules and the concurrent reduction in the energy requirement for the ring-opening process of benzoic acid on the TiO2 (001) surface. Moreover, the TiO2 (001) surface generated a greater number of reactive oxygen species (ROS), thereby promoting the separation of photogenerated charge carriers and concurrently diminishing their recombination rates, amplifying the efficiency of photocatalysis. This research provides an innovative perspective for a more comprehensive understanding of the photocatalytic degradation mechanism of TiO2 and presents promising prospects for significant applications in environmental purification and energy fields.

Understanding the Poly (Triazine Imide) Crystals Formation Process: The Conversion from Heptazine to Triazine.

Poly (triazine imide) (PTI) generally obtained via ionothermal synthesis features extended π-conjugation and enhanced crystallinity. However, in-depth investigation of the polycondensation process for PTI is an onerous task due to multiple influencing factors and limited characterization techniques. Herein, to simplify the polymerization route and exclude non-essential factors, PTI was prepared by calcining only melamine and LiCl. This study aims to identify the pivotal role of LiCl in PTI formation, which can convert heptazine-based intermediates into more stable triazine-based PTI framework. Based on this discovery, we demonstrate the transformation process of the prepared samples from amorphous Bulk g-C3 N4 to regular PTI, and further prove that the reaction with LiCl causes disruption of heptazine covalent organic frameworks. Additionally, the PTI exhibits higher photocatalytic water splitting performance due to efficient charge carrier mobility and separation, as well as faster reaction kinetics. This discovery deepens understanding of the polycondensation process of PTI crystals and provides insights toward the rational design of crystalline carbon nitride-based semiconductors.

Photocatalytic Z-scheme Overall Water Splitting: Insight into Different Optimization Strategies for Powder Suspension and Particulate Sheet Systems.

Achieving solar light-driven photocatalytic overall water splitting is the ideal and ultimate goal for solving energy and environment issues. Photocatalytic Z-scheme overall water splitting has undergone considerable development in recent years; specific approaches include a powder suspension Z-scheme system with a redox shuttle and a particulate sheet Z-scheme system. Of these, a particulate sheet has achieved a benchmark solar-to-hydrogen efficiency exceeding 1.1 %. Nevertheless, owing to intrinsic differences in the components, structure, operating environment, and charge transfer mechanism, there are several differences between the optimization strategies for a powder suspension and particulate sheet Z-scheme. Unlike a powder suspension Z-scheme with a redox shuttle, the particulate sheet Z-scheme system is more like a miniaturized and parallel p/n photoelectrochemical cell. In this review, we summarize the optimization strategies for a powder suspension Z-scheme with a redox shuttle and particulate sheet Z-scheme. In particular, attention has been focused on choosing appropriate redox shuttle and electron mediator, facilitating the redox shuttle cycle, avoiding redox mediator-induced side reactions, and constructing a particulate sheet. Challenges and prospects in the development of efficient Z-scheme overall water splitting are also briefly discussed.

In Situ Growth Facilitating the Piezo-Photocatalytic Effect of Zn1-xCdxS/ZnO Nanorods for Highly Efficient H2 Production.

Photocatalytic H2 production holds promise for alleviating energy and environmental issues. The separation of photoinduced charge carriers plays vital roles in enhancing the activity of photocatalytic H2 production. The piezoelectric effect has been proposed to be effective in facilitating the separation of charge carriers. However, the piezoelectric effect is usually restricted by the noncompact contact between the polarized materials and semiconductors. In this study, Zn1-xCdxS/ZnO nanorod arrays on stainless steel for piezo-photocatalytic H2 production are fabricated by an in situ growth method, achieving an electronic-level contact between Zn1-xCdxS and ZnO. The separation and migration of photogenerated charge carriers in Zn1-xCdxS are significantly improved by the piezoelectric effect induced by ZnO under mechanical vibration. Consequently, under solar and ultrasonic irradiation, the H2 production rate of Zn1-xCdxS/ZnO nanorod arrays achieves 20.96 µmol h-1 cm-2, which is 4 times higher than that under solar irradiation. Such a performance can be attributed to the synergies of the piezoelectric field of bent ZnO nanorods and the built-in electric field of the Zn1-xCdxS/ZnO heterostructure, which efficiently separate the photoinduced charge carriers. This study provides a new strategy to couple polarized materials and semiconductors for highly efficient piezo-photocatalytic H2 production.

Enhanced Photocatalytic Hydrogen Production of ZnIn2S4 by Using Surface-Engineered Ti3C2Tx MXene as a Cocatalyst.

Developing efficient and stable photocatalysts is crucial for photocatalytic hydrogen production. Cocatalyst loading is one of the effective strategies for improving photocatalytic efficiency. Here, Ti3C2Tx (Tx = F, OH, O) nanosheets have been adopted as promising cocatalysts for photocatalytic hydrogen production due to their metallic conductivity and unique 2D characterization. In particular, surface functionalized Ti3C2(OH)x and Ti3C2Ox cocatalysts were synthesized through the alkalization treatment with NaOH and a mild oxidation treatment of Ti3C2Fx, respectively. ZnIn2S4/Ti3C2Tx composites, which were fabricated by the in-situ growth of ZnIn2S4 nanosheets on the Ti3C2Tx surface, exhibited the promoted photocatalytic performance, compared with the parent ZnIn2S4. The enhanced photocatalytic performance can be further optimized through the surface functionalization of Ti3C2Fx. As a result, the optimized ZnIn2S4/Ti3C2Ox composite with oxygen functionalized Ti3C2Ox cocatalyst demonstrated excellent photocatalytic hydrogen evolution activity. The characterizations and density functional theory calculation suggested that O-terminated Ti3C2Ox could effectively facilitate the transfer and separation of photogenerated electrons and holes due to the formation of a Schottky junction, with the largest difference in work function between ZnIn2S4 and Ti3C2Ox. This work paves the way for photocatalytic applications of MXene-based photocatalysts by tuning their surface termination groups.

Construction of TiO2 /SrTiO3 Heterojunction Derived from Monolayer Ti3 C2 MXene for Efficient Photocatalytic Overall Water Splitting.

Construction of heterojunction at the atomic scale to ensure efficient charge separation for improvement of photocatalytic water splitting is challenging. Herein, a facile hydrothermal method has been applied for the in situ fabrication of TiO2 /SrTiO3 heterojunction, using the monolayer Ti3 C2 MXene as the template and reactant. It is found that the sample with the hydrothermal reaction time of 60 min exhibits the highest H2 evolution rate with the sacrificial reagent, due to the efficient charge separation of TiO2 /SrTiO3 heterojunction as Ti3 C2 derivative. In addition, the sample shows the best overall water splitting performance at a hydrothermal reaction time of 120 min, where TiO2 is nearly converted to SrTiO3 , due to the fast kinetic process and low structural defects of SrTiO3 . This work not only provides a simple strategy for the fabrication of heterojunction photocatalysts but also demonstrates the difference in optimization of half-reaction and overall water splitting reaction.

Piezoelectric built-in electric field advancing TiO2 for highly efficient photocatalytic air purification.

Photocatalytic air purification is a promising technology; however, it suffers from a limited rate of photocatalytic mineralization (easily inactivated surfactant sites of hydroxyls) and poor kinetics of degradation. Herein, we report a ferroelectric strategy, employing a polyvinylidene fluoride (PVDF) layer embedded with TiO2, where the polarization field of stretched PVDF dramatically enhances and stabilizes active adsorption sites for the promotion of charge separation. The F (-) and H (+) atomic layers with distinct local structures in stretched PVDF increase the electron cloud density around Ti which simultaneously promotes the dissociation of water to form hydroxyl groups which are easier to activate for adsorption of formaldehyde molecules. Besides, the ferroelectric field of stretched PVDF effectively separates the photogenerated charge carriers and facilitates the carriers' transportation of TiO2/PVDF. The optimal stretched TiO2/PVDF exhibits excellent photocatalytic mineralization for formaldehyde with considerable stability. This work may evolve the polarization field as a new method to enhance adsorption and activation of hydroxyls and disclose the mechanism by which hydroxyl radicals mineralize gaseous formaldehyde for photocatalytic air purification.

Priority Occupation of C-Sites by N-Confining P-Implantation in Pyrrodic N-Sites in NCNT@P,N-Mo2C for Highly Efficient Electrocatalytic Hydrogen Evolution.

Optimizing the electronic configuration of Mo2C by activating heteroatom(s)-neighboring carbon atoms to enhance the activity of hydrogen evolution reaction (HER) has been demonstrated. However, the development of heteroatom-doped Mo2C to fabricate a water electrolyzer is still a challenge because of the limitation of a well-defined electronic structure of hybridization of Mo with heteroatom(s). Here, nitrogen (N) and phosphor (P) codoped Mo2C embedded carbon nanotubes (NCNT@P,N-Mo2C) with the priority occupation of C-sites by N, which well confines the P-implantation at the pyrrodic N-sites and brings out N-O bonding on the surface, which favorably modifies the electronic configuration of adjacent Mo, resulting in highly efficient pH-tolerant HER activity. This study not only presents a potential HER electrocatalyst candidate but also provides a strategy for the construction of a well-defined electronic structure of heteroatom(s)-neighboring carbon-based materials.

Direct Synthesis of Dimethyl Ether from Syngas Over Hybrid Catalyst with Hierarchical ZSM-5 as the Methanol Dehydration Catalyst.

Commercial ZSM-5 zeolites were submitted to alkaline treatment in order to prepare hierarchical ZSM-5 zeolites with hierarchical porosity and moderate acidity. Hybrid bifunctional catalyst comprising a CuO-ZnO-Al2O3 (CZA) and zeolite was prepared by physical mixing method, used for the direct synthesis of dimethyl ether (DME) from syngas. The correlation between the textural and acid properties of the zeolite and the catalytic performance of hybrid catalyst has been assessed from the combined results of N2 physisorption, FTIR of adsorbed pyridine, elemental analysis ICP, online-GC and other characterization techniques. The results indicate that the hybrid catalyst with hierarchical ZSM-5 zeolite exhibits higher activity and stability than that with parent ZSM-5 zeolite due to the synergy effect of moderated acidity and enhanced mass transport capability of the hierarchical ZSM-5 sample. Under 260 °C, 2.0 MPa and 3600 h-1, the conversion of CO and the DME selectivity to DME over hybrid catalyst CZA-ZSM-5(25)-A achieved 65.2% and 67.8%, respectively.

Oxidative methane reforming with an intelligent catalyst: sintering-tolerant supported nickel nanoparticles.

Smart Catalyst: The cyclical diffusion of nanometer-sized nickel clusters into and out of the perovskite structure under elevated temperature and reducing and oxidizing atmosphere could in situ redeliver and redisperse Ni, thereby reinforcing the anti-coking and -sintering of Ni during oxidative reforming of CH4 .