Ultrathin Fe-MOFs modified by Fe9S10 for highly efficient oxygen evolution reaction.

Developing efficient and economical catalysts is essential for water splitting. The application of MOF catalysts in water splitting is limited by poor conductivity; however, the introduction of conductive TMS could enhance their activity. Herein, novel composite Fe9S10/Fe-MOF/NF-2 was constructed by introducing dendritic Fe9S10 onto the surface of a 2D ultrathin Fe-MOF. Composite catalysts elaborately utilize the structural and chemical advantages of MOF and TMS while improving the deficiencies of monomers through the combination. Owing to the optimal structure, the hybrid catalyst Fe9S10/Fe-MOF/NF-2 displayed better catalytic performance than bare Fe-MOFs and Fe9S10, with low overpotentials of 202 and 216 mV at 10 mA cm-2 in alkaline solution and simulated seawater, respectively. This work provides an innovative approach to modify MOFs as electrocatalysts for OER.

Construction of core-shell CoSe2/ZnIn2S4 heterostructures for efficient visible-light-driven photocatalytic hydrogen evolution.

The use of photocatalysts based on semiconductor heterostructures for hydrogen evolution is a prospective tactic for converting solar energy. Herein, visible-light-responsive three-dimensional core-shell CoSe2/ZnIn2S4 heterostructures were successfully fabricated via in situ growth of ZnIn2S4 ultrathin nanosheets on spherical CoSe2. Without any noble metal co-catalysts, the as-prepared CoSe2/ZnIn2S4 composite achieved attractive photocatalytic hydrogen evolution activity under visible light illumination. Optimal CoSe2/ZnIn2S4 achieved a hydrogen evolution rate of 2199 µmol g-1 h-1, which was 7 times higher than that of pristine ZnIn2S4 and even exceeded that of ZnIn2S4 loaded with platinum. In this distinctive core-shell heterostructure, the presence of CoSe2 could considerably improve the ability to harvest light, quicken the charge transfer kinetics, and avoid the agglomeration of ZnIn2S4 nanosheets. Meanwhile, the experimental results demonstrated that the strong interaction between CoSe2 and ZnIn2S4 at the compact interface could appropriately boost the photogenerated electron-hole pair migration and relieve charge recombination, thus improving photocatalytic hydrogen evolution activity. This work has bright prospects in constructing noble-metal-free core-shell heterostructures for solar energy conversion.

Enhancing charge transfer in a W18O49/g-C3N4 heterostructure via band structure engineering for effective SERS detection and flexible substrate applications.

Chemical mechanism (CM)-related surface-enhanced Raman spectroscopy (SERS) has received tremendous interest due to its exceptional stability and excellent uniformity. Nevertheless, there remains a demand for ingenious methodologies for promoting effective charge transfer (CT) to improve SERS sensitivity further. Herein, a band structure engineered W18O49/g-C3N4 heterostructure (WCN) was first employed as a CM-based SERS substrate with remarkable enhancement and sensitivity. To investigate the Raman enhancement properties of the substrate, malachite green (MG) was employed as the Raman probe with the excitation of a 633 nm laser. The WCN substrate exhibits a Raman enhancement factor (EF) of 2.6 × 107, achieving a limit of detection (LOD) of 1.9 × 10-10 M for MG. The outstanding Raman amplification behavior can be attributed to the heterojunction-induced efficient CT process, energy band matching resonance due to minor doping with g-C3N4 serving as a band gap modifier, and improved photo-induced charge transfer (PICT) efficiency via the oxygen vacancies in the W18O49 units. Additionally, a flexible SERS substrate based on WCN was constructed using a vacuum filtration method and utilized to detect prohibited pharmaceutical residues on fish skin. The integration of this WCN and a nylon membrane not only preserves the Raman activity of the WCN for sensitive detection but also endows the Raman substrate with high flexibility and good mechanical durability, making it a potential candidate for in situ detection in particular environments.

High-performance SERS chips for sensitive identification and detection of antibiotic residues with self-assembled hollow Ag octahedra.

High-performance SERS chips via self-assembled hollow Ag octahedra on PDMS were employed to achieve the sensitive identification and detection of antibiotic residues. The developed SERS chips were successfully applied in the detection of ciprofloxacin (CIP), amoxicillin (AMX) and cefazolin (CZL) in wastewater and tap water samples, as well as enrofloxacin (ENR) in milk, demonstrating the sensitive determination of antibiotics in the real environment. From this perspective, these SERS chips are expected to expand the on spot sensitive detection and identification field of antibiotic residues.

MnOxHy-modified CoMoP/NF nanosheet arrays as hydrogen evolution reaction and oxygen evolution reaction bifunctional catalysts under alkaline conditions.

It is widely acknowledged that interface engineering strategies can significantly enhance the activity of catalysts. In this study, we developed a CoMoP nanoarray directly grown in situ on a nickel foam (NF) substrate, with the interface structure formed through the electrodeposition of MnOxHy. The resulting heterostructure MnOxHy/CoMoP/NF exhibited remarkable hydrogen evolution reaction (HER) activity, achieving overpotentials as low as 61 and 138 mV at 10 and 100 mA cm-2, respectively. Moreover, MnOxHy/CoMoP/NF demonstrated efficient oxygen evolution reaction (OER) activity with an overpotential of 330 mV at 100 mA cm-2. Remarkably, MnOxHy/CoMoP/NF maintained its catalytic properties and structural integrity even after working continuously for 20 h facilitating the HER at 10 mA cm-2 and the OER at 100 mA cm-2. The Tafel slopes of the HER and OER were determined to be as small as 14 and 55 mV dec-1, respectively, confirming that the coupled interface conferred fast reaction kinetics on the catalyst. When applied in overall water splitting, MnOxHy/CoMoP/NF delivered a voltage of 1.91 V at 100 mA cm-2 with excellent stability. This study demonstrated the feasibility of utilizing a simple electrodeposition technique to fabricate a heterogeneous structure with bifunctional catalytic activity, establishing a solid foundation for diverse industrial applications.

2D iron/cobalt metal-organic frameworks with an extended ligand for efficient oxygen evolution reaction.

The design of an efficient OER catalyst is significant for water splitting. Metal-organic frameworks (MOFs) are emerging as promising electrocatalysts due to their diversity of structure and tunability of function. In this paper, 2D FexCo1-x-MOF1/NF with an extended ligand (biphenyl-4,4'-dicarboxylic acid, BPDC) is constructed on nickel foam by a solvothermal method. Compared with the MOF2 synthesized by using BDC (1,4-bezenedicarboxylate), MOF1 shows excellent performance. Among MOF1, Fe0.5Co0.5-MOF1/NF exhibits outstanding performance with a low overpotential (217 mV) and a small Tafel slope (31.16 mV Dec-1) at 10 mA cm-2 and performs well at a high current density. In addition, the catalyst is remarkable in terms of durability both in alkaline solution and simulated seawater. The synergetic effect between Fe and Co and more active sites exposed play an important role in improving the OER activity. This work provides an effective strategy for the rational design of MOFs as inexpensive electrocatalysts.

Methylthio-functionalized UiO-66 to promote the electron-hole separation of ZnIn2S4 for boosting hydrogen evolution under visible light illumination.

Solar-driven water splitting offers a leading-edge approach to storing abundant and intermittent solar energy and producing hydrogen as a clean and sustainable energy carrier. More importantly, constructing well-designed photocatalysts is a promising approach to develop clean hydrogen energy. In this paper, flower spherical UiO-66-(SCH3)2/ZnIn2S4 (UiOSC/ZIS) photocatalysts are successfully synthesized by a simple two-step hydrothermal method, and they exhibit high hydrogen production activity in light-driven water splitting. The optimized 30-UiOSC/ZIS (the content of UiOSC was 30 mg) composite exhibits optimal hydrogen production activity with a hydrogen production of 3433 µmol g-1 h-1, which is 5 and 235 times higher than that of pure ZIS and UiOSC, respectively. In addition, a long-cycling stability test has shown that the UiOSC/ZIS composite has good stability and recyclability. Experimental and characterization results show the formation of a type-II heterojunction between UiOSC and ZIS. This effectively suppresses the recombination of electrons-holes and promotes the carrier transfer, thus significantly improving the hydrogen production performance. This research further promotes the application of UiO-66-(SCH3)2 in the field of photocatalytic hydrogen production and provides a reference for the rational design of UiO-66-based composite photocatalysts.

Robust FeCoP nanoparticles grown on a rGO-coated Ni foam as an efficient oxygen evolution catalyst for excellent alkaline and seawater electrolysis.

Electrochemical water splitting is a potential green hydrogen energy generation technique. With the shortage of fresh water, abundant seawater resources should be developed as the main raw material for water electrolysis. However, since the precipitation reaction of chloride ions in seawater will compete with the oxygen evolution reaction (OER) and corrode the catalyst, seawater electrolysis is restricted by the decrease in activity, low stability, and selectivity. Rational design and development of efficient and stable catalysts is the key to seawater electrolysis. Herein, a high-activity bimetallic phosphide FeCoP, grown on a reduced graphene oxide (rGO)-protected Ni Foam (NF) substrate using FeCo Prussian Blue Analogue (PBA) as a template, was designed for application in alkaline natural seawater electrolysis. The OER activity confirmed that the formed FeCoP@rGO/NF has high electrocatalytic performance. In 1 M KOH and natural alkaline seawater, the overpotential was only 257 mV and 282 mV under 200 mA cm-2, respectively. It also demonstrated long-term stability up to 200 h. Therefore, this study provides new insight into the application of PBA as a precursor of bimetallic phosphide in the electrolysis of seawater at high current density.

Occurrence and removal of conventional pollutants, estrogenicities, and fecal coliform in village sewage treatment plants along the Yangtze River, China.

The present study investigated the occurrence and removal efficiency of some conventional pollutants, estrogenic effects, and fecal coliform in influents and/or effluents of village sewage treatment plants (STPs) in the upper, middle, and lower reaches of the Yangtze River Basin. The water quality of sewage from the village STPs showed significant seasonal and spatial variability. The removal rates of conventional pollutants by the village STPs were mostly lower than urban STPs, thereby resulting in that the water quality compliance rate of the effluents was only 33.3%. In addition, the average removal rate of estrogenic compounds was only 22.2%, which caused the estrogenicity of effluent to exceed the safety threshold. And E2 was determined to be the main estrogenic component. Moreover, ultraviolet (UV) disinfection, as the main disinfection treatment process of sewage along the Yangtze River Basin, was unable to meet the discharge standard of fecal coliform. The sequential chlorine (10 mg L-1)-UV (20 mJ cm-2) disinfection was found to both achieve up-to-standard discharge of fecal coliform and increase the removal rate of estrogenic effect from 3.78 to 9.86%. Overall, the present study provides valuable information on the conventional pollutants, estrogenic effects, and fecal coliform in sewage from village STPs along the Yangtze River Basin, and practical suggestions for basin-wide pollution control.

Self-supported CoMoO4/NiFe-LDH core-shell nanorods grown on nickel foam for enhanced electrocatalysis of oxygen evolution.

Developing high-performance catalysts is an effective strategy for speeding up the oxygen evolution reaction (OER) and increasing production efficiency. Here, a core-shell electrocatalyst consisting of CoMoO4 nanorods grown in situ on nickel foam substrate covered by nickel-iron layered double hydroxide (NiFe-LDH) via electrodeposition was demonstrated (CoMoO4/NiFe-LDH@NF). Experimental investigations revealed that self-supporting and binder-free electrodes ensured that the catalysts exposed an abundance of active sites, faster electron transfer, and excellent long-cycle stability. The NiFe-LDH shell with a crystalline-amorphous dual structure served as an accurate active material, lowering the energy barrier and contributing more catalytic sites for water oxidation. Furthermore, the core CoMoO4 nanorods not only effectively avoided the accumulation of NiFe-LDH to increase the electrochemically active area but also acted as a highway for electrons from the active site to the substrate to promote the OER kinetics. Specifically, CoMoO4/NiFe-LDH@NF exhibited lower overpotential (180 mV at 10 mA cm-2) and smaller Tafel slope (34 mV dec-1) than pure CoMoO4@NF and NiFe-LDH@NF, revealing its excellent catalytic performance and fast intrinsic reaction kinetics. In addition, CoMoO4/NiFe-LDH@NF exhibited long-term stability of more than 20 h at 50 mA cm-2, further demonstrating its potential for practical applications. These findings pointed to a potential option for building innovative OER catalysts.

Ni2P NPs loaded on methylthio-functionalized UiO-66 for boosting visible-light-driven photocatalytic H2 production.

The UiO-66 family shows promising photocatalytic prospects in water splitting for hydrogen evolution under visible light irradiation due to its suitable band gap and adequate active sites. In this work, novel Ni2P/UiO-66-(SCH3)2 composites were prepared by a simple solvothermal method. These as-synthesized samples were fully characterized by XRD, SEM, TEM, HRTEM, EDS, and XPS methods. The effectiveness of visible light driven photocatalytic water-splitting to produce hydrogen was investigated in the presence of sacrificial agents. The results showed that the optimal hydrogen yield of 5 wt% Ni2P/UiO-66-(SCH3)2 is 3724.22 µmol g-1 h-1, reaching almost 187 times that of pristine UiO-66-(SCH3)2 (19.93 µmol g-1 h-1). Meanwhile, long term cycling stability tests also showed that Ni2P/UiO-66-(SCH3)2 composites present an excellent photocatalytic H2 production stability. Photoelectrochemical performance analysis revealed that the high catalytic activity of the composite materials could be associated with the synergistic effect of UiO-66-(SCH3)2 and Ni2P. Light stimulates UiO-66-(SCH3)2 to generate electrons and holes, and Ni2P as a cocatalyst could effectively transmit electrons and boost photogenerated charge separation. This work provides a reference for exploring UiO-66 family catalysts with good catalytic activity.

Directional Damping of Plasmons at Metal-Semiconductor Interfaces.

ConspectusOver the past decade, it has been shown that surface plasmons can enhance photoelectric conversion in photovoltaics, photocatalysis, and other optoelectronic applications through their plasmonic absorption and damping processes. However, plasmonically enhanced devices have yet to routinely match or exceed the efficiencies of traditional semiconductor devices. The effect of plasmonic losses dissipates the absorbed photoenergy mostly into heat and that has hampered the realization of superior next-generation plasmonic optoelectronic devices. Several approaches are being explored to alleviate this situation, including using gain to compensate for the plasmonic losses, designing and synthesizing alternative low-loss plasmonic materials, and reducing activation barriers in plasmonic devices and physical thicknesses of photoabsorber layers to lower the plasmonic losses. A newly proposed plasmon-induced interfacial charge-transfer transition (PIICTT) mechanism has proven to be effective in minimizing energy loss during interfacial charge transfer. The PIICTT leads to a damping of metallic plasmonics by directly generating excitons at the plasmonic metal/semiconductor heteronanostructures. This novel concept has been proven to overcome some of the limitations of electron-transfer inefficiencies, renewing a focus on surface plasmon damping processes with the goal that the plasmonic excitation energies of metal nanoparticles can be more efficiently transferred to the adjacent semiconductor components in the absence and presence of an effective interlayer of carrier-selective blocking layer (CSBL). Several theoretical and experimental studies have concluded that efficient plasmon-induced ultrafast hot-carrier transfer was observed in plasmonic-metal/semiconductor heteronanostructures. The PIICTT mechanism may well be a general phenomenon at plasmonic metal/semiconductor, metal/molecule, semiconductor/semiconductor, and semiconductor/molecule heterointerfaces. Thus, the PIICTT presents a new opportunity to limit energy loss in plasmonic-metal nanostructures and increase device efficiencies based on plasmonic coupling. The nonradiative damping of surface plasmons can impact the energy flux direction and thereby provide a new process beyond light trapping, focusing, and hot carrier creation.In this Account, we draw much attention to the benefits of interfacial plasmonic coupling, highlighting recent pioneering discoveries in which plasmon-induced interfacial charge- and energy-transfer processes enable the generation of hot charge carriers near the plasmonic-metal/semiconductor interfaces. This process is likely to increase the photoelectric conversion efficiency, constituting "plasmonic enhancement". We also discuss recent advances in the dynamics of surface plasmon relaxation and highlight exciting new possibilities for plasmonic metals and their interactions with strongly attached semiconductors to provide directional energy fluxes. While this new research area comes on the heels of much elaborate research on both metal and semiconductor nanomaterials, it provides a subtle but important refinement in understanding the optoelectronic properties of materials with far-reaching consequences from fundamental interface science to technological applications. We hope that this Account will contribute to a more systematic description of interface-coupled plasmonics, both fundamentally and in terms of applications toward the design of plasmonic heterostructured devices.

In-Situ Anchoring Pb-Free Cs3 Bi2 Br9 @BiOBr Quantum Dots on NHx -Rich Silica with Enhanced Blue Emission and Satisfactory Stability for Photocatalytic Toluene Oxidation.

All-inorganic metal halide perovskite quantum dots (QDs) have attracted attention from researchers with their fascinating optoelectronic properties. However, blue-emitting perovskite QDs typically have low photoluminescence quantum yield (PLQY). For potential commercial applications, it is preferable to replace Pb with an element having low toxicity. Here, Pb-free Cs3 Bi2 Br9 @BiOBr perovskite QDs were anchored on the surface of NHx -rich monodisperse silica (A-SiO2 ) via N-Bi chemical bonding to isolate QDs from each other, thus enhancing efficient surface passivation and suppressing optical decay. Compared to unanchored QDs, Cs3 Bi2 Br9 @BiOBr QDs/A-SiO2 composites exhibited significantly enhanced blue emission performance, the PLQY of which increased from 16.62 % to 77.26 %, in addition to good water and environmental stability. Finally, the novel composites as photocatalysts were used to drive the oxidation of toluene, a template reaction of C(sp3 )-H bond activation and demonstrated astonishing conversion rates (4317 µmol g-1  h-1 ) with high selectivity (around 87 %).

Lead-Free Cs2 AgSbCl6 Double Perovskite Nanocrystals for Effective Visible-Light Photocatalytic C-C Coupling Reactions.

Lead halide perovskite nanocrystals (NCs) have been regarded as a promising potential photocatalyst, owing to their high molar extinction coefficient, low economic cost, adjustable light absorption range, and ample surface active sites. However, the toxicity of lead and its inherent instability in water and polar solvents could hinder their wide application in the field of photocatalysis. Herein, with α-alkylation of aldehydes as a model reaction, C-C bond-forming is demonstrated in high yield by using lead-free double perovskite Cs2 AgSbCl6 NCs under visible light irradiation. Moreover, the photocatalytic performance is simply improved by rational control of the surface ligands and a reaction mechanism involving a radical intermediate is proposed. Although the stability requires further amelioration, the results indicate the enormous potential of lead-free double perovskite NC photocatalysts for organic synthesis and chemical transformations.

Amorphous NiCoB-coupled MAPbI3 for efficient photocatalytic hydrogen evolution.

It was thought that the organic-inorganic hybrid perovskite MAPbI3 could be used to collect visible light for the photocatalytic hydrogen evolution reaction (HER). However, its ability to generate H2 is limited. Herein, we synthesized amorphous NiCoB through a redox method and coupled it with MAPbI3 to form the NiCoB/MAPbI3 composite photocatalyst by electrostatic self-assembly. 30% NiCoB/MAPbI3 exhibited the maximum H2 generation yield of 2625.57 µmol g-1 h-1, which was approximately 114 fold that of pristine MAPbI3 and much better than that of Pt/MAPbI3. In addition to the excellent photocatalytic HER capability, NiCoB/MAPbI3 maintained good stability in the 24 h cycling hydrogen evolution experiment. The photoelectric analysis showed that NiCoB as a cocatalyst could realize rapid charge separation. This work can offer a reference for the construction of efficient photocatalysts based on lead halide perovskites.

All-inorganic lead-free metal halide perovskite quantum dots: progress and prospects.

Lead halide perovskite quantum dots have drawn worldwide attention due to their quantum confinement effect and excellent optical gain properties. It is worth noting that due to the toxicity of lead ions and the inherent instability of organic groups, research on all-inorganic lead-free metal halide perovskite quantum dots (ILFHPQDs) has become a hot spot in recent years. This paper summarizes the latest research progress of ILFHPQDs, analyzes the sources and limitations affecting the performance of ILFHPQDs, and provides the improvement methods. Firstly, the typical synthesis strategies of ILFHPQDs are discussed, followed by a focus on the structural characteristics, optoelectronic properties and stability of each type of ILFHPQD. Next, the applications of ILFHPQDs in devices are investigated. Finally, the challenges, solutions and future application directions of ILFHPQDs are prospected.

MoC/MAPbI3 hybrid composites for efficient photocatalytic hydrogen evolution.

Metal halide perovskites, such as iodine methylamine lead (MAPbI3), have received extensive attention in the field of photocatalytic decomposition of HI for hydrogen evolution, due to their excellent photoelectric properties. In this paper, a new MAPbI3-based composite, MoC/MAPbI3, was synthesized. The results show that 15 wt% MoC/MAPbI3 has the best hydrogen production performance (38.4 µmol h-1), which is approximately 24-times that of pure MAPbI3 (1.61 µmol h-1). With the extension of the catalytic time, the hydrogen production rate of MoC/MAPbI3 reached 165.3 µmol h-1 after 16 h due to the effective separation and transfer of charge carriers between MoC and MAPbI3, showing excellent hydrogen evolution rate performance under visible light. In addition, the cycling stability of MoC/MAPbI3 did not decrease in multiple 4 h cycle tests. This study used the non-precious metal promoter MoC to modify MAPbI3, and provides a new idea for the synthesis of efficient MAPbI3-based composite catalysts.

Cu-Sb-S Ternary Semiconductor Nanoparticle Plasmonics.

Semiconductor plasmonics is a recently emerging field that expands the chemical and physical bandwidth of the hitherto well-established noble metallic nanoparticles. Achieving tunable plasmonics from colloidal semiconductor nanocrystals has drawn enormous interest and is promising for plasmon-related applications. However, realizing this goal of tunable semiconductor nanocrystals is currently still a synthetic challenge. Here, we report a colloidal synthesis strategy for highly dispersed, platelet-shaped, antimony-doped copper sulfide semiconductor nanocrystals (Sby-CuxS NCs) with a dominant localized surface plasmon resonance (LSPR) band tunable from the near-infrared into the midvisible spectral range. This work presents the synthesis and quantifies the resulting plasmonic features. It furthermore elucidates the underlying carrier concentration requirements to realize a continuum of LSPR spectra. Building on our previous work on binary plasmonics CuxS, CuxSe, and CuxTe NCs, the present method introduces a much wider and finer tunability with ternary semiconductor plasmonics.

Partial Cu ion exchange induced triangle hexagonal Mn0.45Cu0.05Cd0.5S nanocrystals for enhanced photocatalytic hydrogen evolution.

High crystallinity triangle hexagonal Mn0.45Cu0.05Cd0.5S was obtained by partial Cu ion exchange treatment on colloidal pristine Mn0.5Cd0.5S nanorods. The Mn0.45Cu0.05Cd0.5S nanotriangles exhibited a high hydrogen yield of 147 921 µmol g-1 h-1 under visible light irradiation, about 7.4 times higher than that of pristine Mn0.5Cd0.5S.

Chiral Proline-Decorated Bifunctional Pd@NH2-UiO-66 Catalysts for Efficient Sequential Suzuki Coupling/Asymmetric Aldol Reactions.

The design and development of site-isolating and multifunctional catalysts for multistep sequential reactions at the molecular level is a significant challenge. Herein, we first report bifunctional metal NPs@chiral MOFs catalysts for asymmetric sequential reactions. Pd nanoparticles and chiral proline were successfully added to NH2-UiO-66 to construct two chiral bifunctional catalysts, in which active Pd nanoparticles were encapsulated into the frameworks via the "bottle-around-ship" method, and chiral proline was introduced into NH2-UiO-66 by coordination to zirconium nodes and postsynthetic modification (PSM) of the organic linkers. The chiral proline-decorated bifunctional Pd@NH2-UiO-66 catalysts were applied to sequential Suzuki coupling/asymmetric aldol reactions with excellent coupling performance (yields up to 99.9%) and good enantioselectivities (eeanti values up to 97%). The heterogeneous catalyst by coordination of proline can be reused, and the reaction activity was not significantly reduced after four cycles.