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.

Amino-Induced CO2 Spillover to Boost the Electrochemical Reduction Activity of CdS for CO Production.

A considerable challenge in CO2 reduction reaction (CO2RR) to produce high-value-added chemicals comes from the adsorption and activation of CO2 to form intermediates. Herein, an amino-induced spillover strategy aimed at significantly enhancing the CO2 adsorption and activation capabilities of CdS supported on N-doped mesoporous hollow carbon sphere (NH2-CdS/NMHCS) for highly efficient CO2RR is presented. The prepared NH2-CdS/NMHCS exhibits a high CO Faradaic efficiency (FECO) exceeding 90% from -0.8 to -1.1 V versus reversible hydrogen electrode (RHE) with the highest FECO of 95% at -0.9 V versus RHE in H cell. Additional experimental and theoretical investigations demonstrate that the alkaline -NH2 group functions as a potent trapping site, effectively adsorbing the acidic CO2, and subsequently triggering CO2 spillover to CdS. The amino modification-induced CO2 spillover, combined with electron redistribution between CdS and NMHCS, not only readily achieves the spontaneous activation of CO2 to *COOH but also greatly reduces the energy required for the conversion of *COOH to *CO intermediate, thus endowing NH2-CdS/NMHCS with significantly improved reaction kinetics and reduced overpotential for CO2-to-CO conversion. It is believed that this research can provide valuable insights into the development of electrocatalysts with superior CO2 adsorption and activation capabilities for CO2RR application.

D-A Conjugated Polymer/CdS S-Scheme Heterojunction with Enhanced Interfacial Charge Transfer for Efficient Photocatalytic Hydrogen Generation.

Owing to the improved charge separation and maximized redox capability of the system, Step-scheme (S-scheme) heterojunctions have garnered significant research attention for efficient photocatalysis of H2 evolution. In this work, an innovative linear donor-acceptor (D-A) conjugated polymer fluorene-alt-(benzo-thiophene-dione) (PFBTD) is coupled with the CdS nanosheets, forming the organic-inorganic S-scheme heterojunction. The CdS/PFBTD (CP) composite exhibits an impressed hydrogen production rate of 7.62 mmol g-1  h-1 without any co-catalysts, which is ≈14 times higher than pristine CdS. It is revealed that the outstanding photocatalytic performance is attributed to the formation of rapid electron transfer channels through the interfacial Cd─O bonding as evidenced by the density functional theory (DFT) calculations and in situ X-ray photoelectron spectroscopy (XPS) analysis. The charge transfer mechanism involved in S-scheme heterojunctions is further investigated through the photo-irradiated Kelvin probe force microscopy (KPFM) analysis. This work provides a new point of view on the mechanism of interfacial charge transfer and points out the direction of designing superior organic-inorganic S-scheme heterojunction photocatalysts.

Non-Noble Plasmonic Metal-Based Photocatalysts.

Solar-to-chemical energy conversion via heterogeneous photocatalysis is one of the sustainable approaches to tackle the growing environmental and energy challenges. Among various promising photocatalytic materials, plasmonic-driven photocatalysts feature prominent solar-driven surface plasmon resonance (SPR). Non-noble plasmonic metals (NNPMs)-based photocatalysts have been identified as a unique alternative to noble metal-based ones due to their advantages like earth-abundance, cost-effectiveness, and large-scale application capability. This review comprehensively summarizes the most recent advances in the synthesis, characterization, and properties of NNPMs-based photocatalysts. After introducing the fundamental principles of SPR, the attributes and functionalities of NNPMs in governing surface/interfacial photocatalytic processes are presented. Next, the utilization of NNPMs-based photocatalytic materials for the removal of pollutants, water splitting, CO2 reduction, and organic transformations is discussed. The review concludes with current challenges and perspectives in advancing the NNPMs-based photocatalysts, which are timely and important to plasmon-based photocatalysis, a truly interdisciplinary field across materials science, chemistry, and physics.

Single-Atom Iron Can Steer Atomic Hydrogen toward Selective Reductive Dechlorination: Implications for Remediation of Chlorinated Solvents-Impacted Groundwater.

Atomic hydrogen (H*) is a powerful and versatile reductant and has tremendous potential in the degradation of oxidized pollutants (e.g., chlorinated solvents). However, its application for groundwater remediation is hindered by the scavenging side reaction of H2 evolution. Herein, we report that a composite material (Fe0@Fe-N4-C), consisting of zerovalent iron (Fe0) nanoparticles and nitrogen-coordinated single-atom Fe (Fe-N4), can effectively steer H* toward reductive dechlorination of trichloroethylene (TCE), a common groundwater contaminant and primary risk driver at many hazardous waste sites. The Fe-N4 structure strengthens the bond between surface Fe atoms and H*, inhibiting H2 evolution. Nonetheless, H* is available for dechlorination, as the adsorption of TCE weakens this bond. Interestingly, H* also enhances electron delocalization and transfer between adsorbed TCE and surface Fe atoms, increasing the reactivity of adsorbed TCE with H*. Consequently, Fe0@Fe-N4-C exhibits high electron selectivity (up to 86%) toward dechlorination, as well as a high TCE degradation kinetic constant. This material is resilient against water matrix interferences, achieving long-lasting performance for effective TCE removal. These findings shed light on the utilization of H* for the in situ remediation of groundwater contaminated with chlorinated solvents, by rational design of earth-abundant metal-based single-atom catalysts.

Molecularly Tunable Heterostructured Co-Polymers Containing Electron-Deficient and -Rich Moieties for Visible-Light and Sacrificial-Agent-Free H2O2 Photosynthesis.

As an alternative to hydrogen peroxide (H2O2) production by complex anthraquinone oxidation process, photosynthesis of H2O2 from water and oxygen without sacrificial agents is highly demanded. Herein, a covalently connected molecular heterostructure is synthesized via sequential C-H arylation and Knoevenagel polymerization reactions for visible-light and sacrificial-agent-free H2O2 synthesis. The subsequent copolymerization of the electron-deficient benzodithiophene-4,8-dione (BTD) and the electron-rich biphenyl (B) and p-phenylenediacetonitrile (CN) not only expands the π-conjugated domain but also increases the molecular dipole moment, which largely promotes the separation and transfer of the photoinduced charge carriers. The optimal heterostructured BTDB-CN0.2 manifested an impressive photocatalytic H2O2 production rate of 1920 µmol g-1 h-1, which is 2.2 and 11.6 times that of BTDB and BTDCN. As revealed by the femtosecond transient absorption (fs-TA) and theoretical calculations, the linkage serves as a channel for the rapid transfer of photogenerated charge carriers, enhancing the photocatalytic efficiency. Further, in situ diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS) uncovers that the oxygen reduction reaction occurs through the step one-electron pathway and the mutual conversion between C=O and C-OH with the anchoring of H+ during the catalysis favored the formation of H2O2. This work provides a novel perspective for the design of efficient organic photocatalysts.

Dynamics of Electron Transfer in CdS Photocatalysts Decorated with Various Noble Metals.

To address charge recombination in photocatalysis, the prevalent approach involves the use of noble metal cocatalysts. However, the precise factors influencing this performance variability based on cocatalyst selection have remained elusive. In this study, CdS hollow spheres loaded with distinct noble metal nanoparticles (Pt, Au, and Ru) are investigated by femtosecond transient absorption (fs-TA) spectroscopy. A more pronounced internal electric field leads to the creation of a larger Schottky barrier, with the order Pt-CdS > Au-CdS > Ru-CdS. Owing to these varying Schottky barrier heights, the interface electron transfer rate (Ke ) and efficiency (ηe ) of metal-CdS in acetonitrile (ACN) exhibit the following trend: Ru-CdS > Au-CdS > Pt-CdS. However, the trends of Ke and ηe for metal-CdS in water are different (Ru-CdS > Pt-CdS > Au-CdS) due to the influence of water, leading to the consumption of photogenerated electrons and affecting the metal/CdS interface state. Although Ru-CdS displays the highest Ke and ηe , its overall photocatalytic performance, particularly in H2 production, lags behind that of Pt-CdS due to the electron backflow from Ru to CdS. This work offers a fresh perspective on the origin of performance differences and provides valuable insights for cocatalyst design and construction.

Single-Atom Engineering of Covalent Organic Framework for Photocatalytic H2 Production Coupled with Benzylamine Oxidation.

In photocatalysis, reducing the exciton binding energy and boosting the conversion of excitons into free charge carriers are vital to enhance photocatalytic activity. This work presents a facile strategy of engineering Pt single atoms on a 2D hydrazone-based covalent organic framework (TCOF) to promote H2 production coupled with selective oxidation of benzylamine. The optimised TCOF-Pt SA photocatalyst with 3 wt% Pt single atom exhibited superior performance to TCOF and TCOF-supported Pt nanoparticle catalysts. The production rates of H2 and N-benzylidenebenzylamine over TCOF-Pt SA3 are 12.6 and 10.9 times higher than those over TCOF, respectively. Empirical characterisation and theoretical simulation showed that the atomically dispersed Pt is stabilised on the TCOF support through the coordinated N1 -Pt-C2 sites, thereby induing the local polarization and improving the dielectric constant to reach the low exciton binding energy. These phenomena led to the promotion of exciton dissociation into electrons and holes and the acceleration of the separation and transport of photoexcited charge carriers from bulk to the surface. This work provides new insights into the regulation of exciton effect for the design of advanced polymer photocatalysts.

Atomic Interface Engineering of Single-Atom Pt/TiO2 -Ti3 C2 for Boosting Photocatalytic CO2 Reduction.

Solar-driven CO2 conversion into valuable fuels is a promising strategy to alleviate the energy and environmental issues. However, inefficient charge separation and transfer greatly limits the photocatalytic CO2 reduction efficiency. Herein, single-atom Pt anchored on 3D hierarchical TiO2 -Ti3 C2 with atomic-scale interface engineering is successfully synthesized through an in situ transformation and photoreduction method. The in situ growth of TiO2 on Ti3 C2 nanosheets can not only provide interfacial driving force for the charge transport, but also create an atomic-level charge transfer channel for directional electron migration. Moreover, the single-atom Pt anchored on TiO2 or Ti3 C2 can effectively capture the photogenerated electrons through the atomic interfacial PtO bond with shortened charge migration distance, and simultaneously serve as active sites for CO2 adsorption and activation. Benefiting from the synergistic effect of the atomic interface engineering of single-atom Pt and interfacial TiOTi, the optimized photocatalyst exhibits excellent CO2 -to-CO conversion activity of 20.5 µmol g-1  h-1 with a selectivity of 96%, which is five times that of commercial TiO2 (P25). This work sheds new light on designing ideal atomic-scale interface and single-atom catalysts for efficient solar fuel conversation.

Additive-mediated intercalation and surface modification of MXenes.

2D carbides and nitrides of transition metals, also known as MXenes, are an emerging class of 2D nanomaterials that have shown excellent performances and broad application prospects in the fields of energy storage, catalysis, sensing, electromagnetic shielding, electronics and photonics, and life sciences. This unusual diversity of applications is due to their superior hydrophilicity and conductivity, high carrier concentration, ultra-high volumetric capacitance, rich surface chemistry, and large specific surface area. However, it is difficult to make MXenes with the desired surface functional groups that deliver high reactivity and high stability, because most MXenes are extracted from ceramics (MAX phase) by an etching process, where a large number of metal atoms are inevitably exposed on the surface, with other anions and cations embedded uncontrollably. The exposed metal atoms and implanted ions are thermodynamically unstable and readily react with trace oxygen or oxygen-containing groups to form the corresponding metal oxides or degrade chemically, resulting in a sharp decline in activity and loss of excellent physicochemical properties. The addition of certain synergistic additives during the intercalation and chemical modification of surface functional groups under non-hazardous conditions can result in stable and efficient MXene-based materials with exceptional optical, electrical, and magnetic properties. This review discusses several such methods, mainly additive-mediated intercalation and chemical modification of the surface functional groups of MXene-based materials, followed by their potential applications. Finally, perspectives are given to discuss the future challenges and promising opportunities of this exciting field.

Correction: Additive-mediated intercalation and surface modification of MXenes.

Correction for 'Additive-mediated intercalation and surface modification of MXenes' by Jing Zou et al., Chem. Soc. Rev., 2022, DOI: 10.1039/d0cs01487g.

Verifying the Charge-Transfer Mechanism in S-Scheme Heterojunctions Using Femtosecond Transient Absorption Spectroscopy.

The S-scheme heterojunction is flourishing in photocatalysis because it concurrently realizes separated charge carriers and sufficient redox ability. Steady-state charge transfer has been confirmed by other methods. However, an essential part, the transfer dynamics in S-scheme heterojunctions, is still missing. To compensate, a series of cadmium sulfide/pyrene-alt-difluorinated benzothiadiazole heterojunctions were constructed and the photophysical processes were investigated with femtosecond transient absorption spectroscopy. Encouragingly, an interfacial charge-transfer signal was detected in the spectra of the heterojunction, which provides solid evidence for S-scheme charge transfer to complement the results from well-established methods. Furthermore, the lifetime for interfacial charge transfer was calculated to be ca. 78.6 ps. Moreover, the S-scheme heterojunction photocatalysts exhibit higher photocatalytic conversion of 1,2-diols and H2 production rates than bare cadmium sulfide.

Reversing Free-Electron Transfer of MoS2+x Cocatalyst for Optimizing Antibonding-Orbital Occupancy Enables High Photocatalytic H2 Evolution.

The interaction between a co-catalyst and photocatalyst usually induces spontaneous free-electron transfer between them, but the effect and regulation of the transfer direction on the hydrogen-adsorption energy of the active sites have not received attention. Herein, to steer the free-electron transfer in a favorable direction for weakening S-Hads bonds of sulfur-rich MoS2+x , an electron-reversal strategy is proposed for the first time. The core-shell Au@MoS2+x cocatalyst was constructed on TiO2 to optimize the antibonding-orbital occupancy. Research results reveal that the embedded Au can reverse the electron transfer to MoS2+x to generate electron-rich S(2+δ)- active sites, thus increasing the antibonding-orbital occupancy of S-Hads in the Au@MoS2+x cocatalyst. Consequently, the increase in the antibonding-orbital occupancy effectively destabilizes the H 1s-p antibonding orbital and weakens the S-Hads bond, realizing the expedited desorption of Hads to rapidly generate a lot of visible H2 bubbles. This work delves deep into the latent effect of the photocatalyst carrier on cocatalytic activity.

Rapid Charge Transfer Endowed by Interfacial Ni-O Bonding in S-scheme Heterojunction for Efficient Photocatalytic H2 and Imine Production.

Cooperative coupling of H2 evolution with oxidative organic synthesis is promising in avoiding the use of sacrificial agents and producing hydrogen energy with value-added chemicals simultaneously. Nonetheless, the photocatalytic activity is obstructed by sluggish electron-hole separation and limited redox potentials. Herein, Ni-doped Zn0.2 Cd0.8 S quantum dots are chosen after screening by DFT simulation to couple with TiO2 microspheres, forming a step-scheme heterojunction. The Ni-doped configuration tunes the highly active S site for augmented H2 evolution, and the interfacial Ni-O bonds provide fast channels at the atomic level to lower the energy barrier for charge transfer. Also, DFT calculations reveal an enhanced built-in electric field in the heterojunction for superior charge migration and separation. Kinetic analysis by femtosecond transient absorption spectra demonstrates that expedited charge migration with electrons first transfer to Ni2+ and then to S sites. Therefore, the designed catalyst delivers drastically elevated H2 yield (4.55 mmol g-1 h-1 ) and N-benzylidenebenzylamine production rate (3.35 mmol g-1 h-1 ). This work provides atomic-scale insights into the coordinated modulation of active sites and built-in electric fields in step-scheme heterojunction for ameliorative photocatalytic performance.

Sub-10 nm Corrugated TiO2 Nanowire Arrays by Monomicelle-Directed Assembly for Efficient Hole Extraction.

Precise synthesis of well-ordered ultrathin nanowire arrays with tunable active surface, though attractive in optoelectronics, remains challenging to date. Herein, well-aligned sub-10 nm TiO2 nanowire arrays with controllable corrugated structure have been synthesized by a unique monomicelle-directed assembly method. The nanowires with an exceptionally small diameter of ∼8 nm abreast grow with an identical adjacent distance of ∼10 nm, forming vertically aligned arrays (∼800 nm thickness) with a large surface area of ∼102 m2 g-1. The corrugated structure consists of bowl-like concave structures (∼5 nm diameter) that are closely arranged along the axis of the ultrathin nanowires. And the diameter of the concave structures can be finely manipulated from ∼2 to 5 nm by simply varying the reaction time. The arrays exhibit excellent charge dynamic properties, leading to a high applied bias photon-to-current efficiency up to 1.4% even at a very low potential of 0.41 VRHE and a superior photocurrent of 1.96 mA cm-2 at 1.23 VRHE. Notably, an underlying mechanism of the hole extraction effect for concave walls is first clarified, demonstrating the exact role of concave walls as the hole collection centers for efficient water splitting.

Semiconductor Gas Sensor for Triethylamine Detection.

With the demanding detection of unique toxic gas, semiconductor gas sensors have attracted tremendous attention due to their intriguing features, such as, high sensitivity, online detection, portability, ease of use, and low cost. Triethylamine, a typical gas of volatile organic compounds, is an important raw material for industrial development, but it is also a hazard to human health. This review presents a concise compilation of the advances in triethylamine detection based on chemiresistive sensors. Specifically, the testing system and sensing parameters are described in detail. Besides, the sensing mechanism with characterizing tactics is analyzed. The research status based on various chemiresistive sensors is also surveyed. Finally, the conclusion and challenges, as well as some perspectives toward this area, are presented.

Inorganic Metal-Oxide Photocatalyst for H2 O2 Production.

Hydrogen peroxide (H2 O2 ) is a mild but versatile oxidizing agent with extensive applications in bleaching, wastewater purification, medical treatment, and chemical synthesis. The state-of-art H2 O2 production via anthraquinone oxidation is hardly considered a cost-efficient and environment-friendly process because it requires high energy input and generates hazardous organic wastes. Photocatalytic H2 O2 production is a green, sustainable, and inexpensive process which only needs water and gaseous dioxygen as the raw materials and sunlight as the power source. Inorganic metal oxide semiconductors are good candidates for photocatalytic H2 O2 production due to their abundance in nature, biocompatibility, exceptional stability, and low cost. Progress has been made to enhance the photocatalytic activity toward H2 O2 production, however, H2 O2 photosynthesis is still in the laboratory research phase since the productivity is far from satisfaction. To inspire innovative ideas for boosting the H2 O2 yield in photocatalysis, the most well-studied metal oxide photocatalysts are selected and the modification strategies to improve their activity are listed. The mechanisms for H2 O2 production over modified photocatalysts are discussed to highlight the facilitating role of the modification methods. Besides, methods for the quantification of H2 O2 and associated radical intermediates are provided to guide future studies in this field.

Low-Temperature-Processed Monolayer Inverse Opal SnO2 Scaffold for Efficient Perovskite Solar Cells.

Organic-inorganic halide perovskite solar cells (PSCs) have attracted tremendous attention in the photovoltaic field due to their excellent optical properties and simple fabrication process. However, the recombination of photogenerated electron-hole pairs at the interface severely affects the power conversion efficiency (PCE) of the PSCs. Herein, a monolayer of inverse opal SnO2 (IO-SnO2 ) is synthesized via a template-assisted method and used as a scaffold for perovskite layer (PSK). The porous IO-SnO2 scaffold increases the contact area and shortens the transport distance between the electron transport layer (ETL) and PSK. Ultraviolet photoelectron spectroscopy and Kelvin probe force microscopy results indicate that the built-in electric field is enhanced with IO-SnO2 scaffold, strengthening the driving force for charge separation. Femtosecond transient absorption spectroscopy measurements reveal that the IO-SnO2 scaffold facilitates interfacial electron transfer from PSK to ETL. Based on the above superiorities, the IO-SnO2 -based PSCs exhibit boosted PCE and device stability compared with the pristine PSCs. This work provides insights into the development of novel scaffold layers for high-performance PSCs.

Calcination-regulated Microstructures of Donor-Acceptor Polymers towards Enhanced and Stable Photocatalytic H2 O2 Production in Pure Water.

Regulating molecular structure of donor-acceptor (D-A) polymer is a promising strategy to improve photoactivity. Herein, a porous nanorod-like D-A polymer is synthesized via a strategy of supramolecular chemistry combined with subsequent calcination treatment. This polymer consists of benzene rings (D) and triazine (A) that are linked by amido bond (-CONH-). -CONH- further partially cracks into cyano groups (-C≡N) (A) under calcination. The ratio of benzene to triazine could be tuned to adjust the -C≡N content by varying the calcination atmosphere. Such regulation of molecular structure could modulate the band structure of D-A polymer and endow it with unique porous nanorod-like morphology, leading to the achievement of two-electron oxygen reduction and two-electron water oxidation and the improvement of exciton splitting, O2 adsorption and activation. These merits synergistically ensure a highly efficient and stable photocatalytic H2 O2 production in pure water.

A Bifunctional CdS/MoO2 /MoS2 Catalyst Enhances Photocatalytic H2 Evolution and Pyruvic Acid Synthesis.

The best use of photogenerated electrons and holes is crucial to boosting photocatalytic activity. Herein, a bifunctional dual-cocatalyst-modified photocatalyst is constructed based on CdS/MoO2 /MoS2 hollow spheres for hydrogen evolution coupled with selective pyruvic acid (PA) production from lactic acid (LA) oxidation. MoS2 and MoO2 are simultaneously obtained from the conversion of CdMoO4 in one step. In a photocatalytic process, the MoS2 and MoO2 function as the reduction and oxidation centers on which photogenerated electrons and holes accumulate and are used for hydrogen evolution reaction (HER) and PA synthesis, respectively. By monitoring the intermediates, a two-step single-electron route for PA production is proposed, initiated by the cleavage of the α-C(sp3 )-H bond in the LA. The conversion of LA and the selectivity of PA can reach ca. 29 % and 95 % after a five-hour reaction, respectively.