Photothermal-Enhanced S-Scheme Heterojunction of Hollow Core-Shell FeNi2 S4 @ZnIn2 S4 toward Photocatalytic Hydrogen Evolution.

Herein, guided by the results of density functional theory prediction, the study rationally designs a hollow core-shell FeNi2 S4 @ZnIn2 S4 (FNS@ZIS) Step-scheme (S-scheme) heterojunction for photocatalytic H2 evolution with photothermal-assisted. The hollow FNS spheres offered substrate for coating the ZIS nanosheets, which can inhibit ZIS nanosheets from agglomerating into pellet, enrich the active site, increase specific surfaces, and raise the light absorption. Notably, due to its excellent photothermal properties, FNS core generated heat unceasingly inside under visible-light irradiation and effectively prevent the heat loss of the reaction system, which increased the local temperature of photocatalysts and thus accelerated the charge migration. In addition, the S-scheme heterojunction construction via in situ growth has a tight interface, which can facilitate the separation and transfer of carriers and achieve high redox potential. Owning to the distinctive construction, the hollow core-shell FNS@ZIS S-scheme heterojunction show extraordinary stability and photocatalytic H2 evolution rate with 7.7 mmol h-1  g-1 , which is ≈15.2-fold than pristine ZIS. Based on the double evidence of theoretical predictions and experimental confirmations, the photothermal effect and electron transfer mechanism of this innovative material are investigated in depth by the following infrared thermography technology and deep DFT calculations.

Enhanced piezo-photocatalytic performance in ZnIn2S4/BiFeO3 heterojunction stimulated by solar and mechanical energy for efficient hydrogen evolution.

An emerging approach that employs both light and vibration energy on binary photo-/piezoelectric semiconductor materials for efficient hydrogen (H2) evolution has garnered considerable attention. ZnIn2S4 (ZIS) is recognized as a promising visible-light-activated photocatalyst. However, its effectiveness is constraint by the slow separation dynamics of photoexcited carriers. Density functional theory (DFT) predictions have shown that the integration of piezoelectric BiFeO3 (BFO) is conducive to the reduction of the H2 adsorption free energy (ΔGH*) for the photocatalytic H2 evolution reaction, thereby enhancing the reaction kinetics. Informed by theoretical predictions, piezoelectric BFO polyhedron particles were successfully synthesized and incorporated with ZIS nanoflowers to create a ZIS/BFO heterojunction using an ultrasonic-assisted calcination method. When subjected to simultaneous ultrasonic treatment and visible-light irradiation, the optimal ZIS/BFO piezoelectric enhanced (piezo-enhanced) heterojunction exhibited a piezoelectric photocatalytic (piezo-photocatalytic) H2 evolution rate approximately 6.6 times higher than that of pristine ZIS and about 3.0 times greater than the rate achieved under light-only conditions. Moreover, based on theoretical predictions and experimental results, a plausible mechanism and charge transfer route for the enhancement of piezo-photocatalytic performance were studied by the subsequent piezoelectric force microscopy (PFM) measurements and DFT calculations. The findings of this study strongly confirm that both the internal electric field of the step-scheme (S-Scheme) heterojunction and the alternating piezoelectric field generated by the vibration of BFO can enhance the transportation and separation of electron-hole pairs. This study presents a concept for the multipath utilization of light and vibrational energy to harness renewable energy from the environment.

Synthesize magnetic ZnFe2O4@C/Cd0.9Zn0.1S catalysts with S-scheme heterojunction to achieve extraordinary hydrogen production efficiency.

Suppressing the electron-hole recombination rate of catalyst legitimately is one of the effective strategies to improve photocatalytic hydrogen evolution. Herein, carbon-coated metal oxide, ZnFe2O4@C (ZFO@C), nanoparticles were synthesized and employed to couple with quadrupedal Cd0.9Zn0.1S (CZS) via an ordinary ultrasonic self-assembly method combined with calcination to form a novel ZFO@C/CZS catalyst with step-scheme (S-scheme) heterojunction. The photocatalytic hydrogen evolution reaction (HER) was conducted to verify the enhanced photoactivity of ZFO@C/CZS. The optimal ZFO@C/CZS exhibits an extraordinary photocatalytic HER rate of 111.3 ± 0.9 mmol g-1 h-1 under visible-light irradiation, corresponding to an apparent quantum efficiency as high as (76.2 ± 0.9)% at 450 nm. Additionally, the as-synthesized ZFO@C/CZS composite exhibits high stability and recyclability. The excellent photocatalytic hydrogen evolution performance should arise from the formed S-scheme heterojunction and the unique ZFO@C core-shell structure, which inhibit electron hole recombination as well as provide more reactive sites. The pathway of S-scheme charge transfer was validated through density functional theory calculations and electrochemical measurements. This work provides a rational strategy for the synthesis of unique magnetic S-scheme heterojunction photocatalysts for water splitting under visible light irradiation.

A novel SnIn4S8/ZnFe2O4 S-scheme heterojunction with excellent magnetic properties and photocatalytic degradation activity for tetracycline.

The development of efficient and economical photocatalysts is considered a promising strategy for pollution remediation. Magnetically separable SnIn4S8/ZnFe2O4 composites (SIS/ZFO) were prepared by combining SIS with ZFO. The composite with a 30% ZFO mass ratio (SIS/ZFO-30) was the most effective and achieved 60% removal of tetracycline (TC) in 120 min. It has a rate constant of 7.94 × 10-3 min-1, which is 6.3 and 27.2 times higher than those of pure SIS and pure ZFO, respectively. The improved photocatalytic performance can be attributed to the formation of S-scheme heterojunctions between SIS and ZFO, which results in the strong absorption of visible light, the enhanced separation of electron-hole pairs, and the higher redox ability of photoinduced charges. Additionally, SIS/ZFO composites have excellent magnetic properties and high stability, and the recovered samples still retained good photocatalytic degradation performances after four cycles of experiments. Thus, the coupling of SIS with ZFO provides a valuable strategy for enhancing photocatalytic potential and offers a promising pathway for water remediation.

Separable alginate gel spheres encapsulated with La-Fe modified biochar for efficient adsorption of Sb(III) with high capacity.

Sb and its compounds have been widely used in various industrial applications. Therefore, the preparation of Sb adsorbents with easy recovery and excellent adsorption levels is an urgent problem that must be resolved. By calcining and treating La/Fe metal-organic frameworks (MOF) biochar as a precursor, a loaded La-Fe-modified water hyacinth biochar was synthesised and used as a filler to synthesise iron alginate composite gel spheres, MBC/algFe. Through a series of static adsorption experiments, the effects of different filler addition ratios, solution pH, reaction time, coexisting ions, and other factors on the adsorption of Sb(III) were investigated. According to the Langmuir model, the maximum adsorption capacity of MBC/algFe at 25 â„ƒ was 277.8 mg·g-1. The adsorption mechanism mainly involved hydrogen bonding and metal-organic complexation interactions.

S-scheme heterojunction of hollow corncob-like ZnIn2S4/LaFeO3 for water splitting and tetracycline degradation.

Reasonable design of heterojunction photocatalysts with high-quality interfacial coupling is an effective way to improve the photocatalytic activity of semiconductors. Herein, we successfully decorated Zinc indium sulfide (ZnIn2S4, ZIS) on perovskite Lanthanum ferrite (LaFeO3, LFO) with more active sites by a pre-hydrothermal combined post-calcination method, and constructed S-scheme heterojunction photocatalyst with a unique hollow corncob-like morphology for efficient photocatalytic hydrogen production and tetracycline (TC) degradation. When the mass ratio of LFO is 35% and 15%, the ZIS/LFO photocatalyst exhibits the best hydrogen evolution rate and TC photodegradation performance, respectively. Notably, the optimum hydrogen production rate is 6 times that of pure ZIS with excellent cycling stability. The enhanced photoactivity can be explained by the hollow corncob-like morphology and the formed S-scheme heterojunction with close interface contact between ZIS and LFO, which significantly improves the spatial separation and migration efficiency of photoexcited carriers, while maintaining a high redox potential. Finally, it provides an effective support for the photocatalytic mechanism through calculation results of density functional theory. This work not only provides a novel construction strategy of photocatalysts for efficient photocatalytic hydrogen evolution and organic pollutant degradation, but also opens up a new insight for perovskite-modified S-scheme heterojunction.

Separable calcium sulphate modified biochar gel beads for efficient cadmium removal from wastewater.

This study outlines the synthesis of a novel, cost-effective composite material comprising calcium sulphate-modified biochar (Ca-BC) cross-linked with polyethyleneimine (PEI) and sodium alginate (SA), which was subsequently transformed into gel beads (Ca-BC@PEI-SA). These beads were engineered to enable effective cadmium ion (Cd(II)) adsorption from wastewater. Batch adsorption experiments were conducted to evaluate the effects of pH, contact time, temperature, and coexisting ions on adsorption performance. The isotherms and kinetics in the adsorption process were investigated. The results indicated that the removal of Cd(II) by Ca-BC@PEI-SA adheres more closely to the Langmuir model, with maximum adsorption capacities of 138.44 mg/g (15 °C), 151.98 mg/g (25 °C), and 165.56 mg/g (35 °C) at different temperatures. The pseudo-secondary model fit well with Cd(II) adsorption kinetics, suggesting that the removal process was a monolayer process controlled by chemisorption. Moreover, the mechanical strength of the Ca-BC@PEI-SA gel beads allowed easy recovery and reduced secondary contamination. In addition, the adsorption capacity remained nearly constant after four cycles. The main Cd(II) adsorption mechanisms involved surface complexation, ion exchange, and cation-π-bonding interactions.

Self-supported P-doped NiFe2O4 micro-sheet arrays for the efficient conversion of nitrite to ammonia.

The nitrite reduction reaction (NO2-RR) is an important process for eliminating toxic nitrites from water while simultaneously producing high-value ammonia under ambient conditions. For the aim to improve the NO2-RR efficiency, we designed a new synthetic strategy to prepare a phosphorus-doped three-dimensional NiFe2O4 catalyst loaded onto a nickel foam in-situ and evaluated its performance for the reduction of NO2- to NH3. The catalyst achieved a high Faradaic efficiency (FE) of 95.39%, and an ammonia (NH3) yield rate of 34788.51 µg h-1 cm-2 at - 0.45 V vs. RHE. A high NH3 yield rate and FE were maintained after 16 cycles at - 0.35 V vs. RHE in an alkaline electrolyte. This study provides a new direction for the rational design of highly stable electrocatalysts for the conversion of NO2- to NH3.

In-situ preparation of mossy tile-like ZnIn2S4/Cu2MoS4 S-scheme heterojunction for efficient photocatalytic H2 evolution under visible light.

The reasonable design and fabrication of heterojunction could regulate the photocatalytic performance to some extent, yet it is still a great challenge to construct the S-scheme heterostructure with the stable as well as tight interface on the surface of semiconductor photocatalysts. Herein, the ZnIn2S4/Cu2MoS4 (ZIS/CMS) S-scheme heterostructure was fabricated by in-situ assembling ZIS nanosheets on the CMS plates, obtaining a mossy tile-like morphology. Owing to the compact interface resulting from in-situ growth, this unique architecture efficiently facilitated the separation and transfer of light-induced charges, guaranteed the larger interface area, and enriched the active sites for photocatalytic redox reactions. After adjusting the mass ratio of CMS in ZIS/CMS, S-scheme heterostructure exhibited the remarkable performance with an optimal H2 producing rate up to 1298 µmol·h-1 g-1, about 13.8 times than that of pristine ZIS. The mechanism and driving force of charge transfer and separation in S-scheme heterostructure photocatalysts were explained and discussed. This investigation will provide new insight into design and construction of S-scheme heterojunction photocatalysts for H2 evolution.

Construction of Zn-doped RuO2 nanowires for efficient and stable water oxidation in acidic media.

Oxygen evolution reaction catalysts capable of working efficiently in acidic media are highly demanded for the commercialization of proton exchange membrane water electrolysis. Herein, we report a Zn-doped RuO2 nanowire array electrocatalyst with outstanding catalytic performance for the oxygen evolution reaction under acidic conditions. Overpotentials as low as 173, 304, and 373 mV are achieved at 10, 500, and 1000 mA cm-2, respectively, with robust stability reaching to 1000 h at 10 mA cm-2. Experimental and theoretical investigations establish a clear synergistic effect of Zn dopants and oxygen vacancies on regulating the binding configurations of oxygenated adsorbates on the active centers, which then enables an alternative Ru-Zn dual-site oxide path of the reaction. Due to the change of reaction pathways, the energy barrier of rate-determining step is reduced, and the over-oxidation of Ru active sites is alleviated. As a result, the catalytic activity and stability are significantly enhanced.

IRSDT: A Framework for Infrared Small Target Tracking with Enhanced Detection.

Currently, infrared small target detection and tracking under complex backgrounds remains challenging because of the low resolution of infrared images and the lack of shape and texture features in these small targets. This study proposes a framework for infrared vehicle small target detection and tracking, comprising three components: full-image object detection, cropped-image object detection and tracking, and object trajectory prediction. We designed a CNN-based real-time detection model with a high recall rate for the first component to detect potential object regions in the entire image. The KCF algorithm and the designed lightweight CNN-based target detection model, which parallelly lock on the target more precisely in the target potential area, were used in the second component. In the final component, we designed an optimized Kalman filter to estimate the target's trajectory. We validated our method on a public dataset. The results show that the proposed real-time detection and tracking framework for infrared vehicle small targets could steadily track vehicle targets and adapt well in situations such as the temporary disappearance of targets and interference from other vehicles.

Achieving improved full-spectrum responsive 0D/3D CuWO4/BiOBr:Yb3+,Er3+ photocatalyst with synergetic effects of up-conversion, photothermal effect and direct Z-scheme heterojunction.

The key to obtain effective photocatalysts is to increase the efficiency of light energy conversion, and thus the design and implementation of full-spectrum photocatalysts is a potential approach to solve this problem especially by extending the absorption range to near-infrared (NIR) light. Herein, the improved full-spectrum responsive CuWO4/BiOBr:Yb3+,Er3+ (CW/BYE) direct Z-scheme heterojunction was prepared. The CW/BYE with CW mass ratio of 5% had the best degradation performance, and the removal rate of tetracycline reached 93.9% in 60 min and 69.4% in 12 h under visible (Vis) and NIR light, respectively, which were 5.2 and 3.3 times of BYE. According to the outcome of experimental, the reasonable mechanism of improved photoactivity was put forward on the basis of (i) the up-conversion (UC) effect of Er3+ ion to convert NIR photon to ultraviolet or visible light, which can be used by CW and BYE, (ii) the photothermal effect of CW to absorb the NIR light, increasing the local temperature of photocatalyst particle to accelerate the photoreaction, and (iii) the formed direct Z-scheme heterojunction between BYE and CW to boost the separation of photogenerated electron-hole pairs. Additionally, the excellent photostability of the photocatalyst was verified by cycle degradation experiments. This work opens up a promising technique for designing and synthesizing full-spectrum photocatalysts by utilizing synergetic effects of UC, photothermal effect and direct Z-scheme heterojunction.

Highly efficient flower-like ZnIn2S4/CoFe2O4 photocatalyst with p-n type heterojunction for enhanced hydrogen evolution under visible light irradiation.

The construction of a p-n heterojunction structure is considered to be an effective method to improve the separation of electron-hole pairs in photocatalysts. A series of ZnIn2S4/CoFe2O4 (ZIS/CFO) photocatalysts with p-n heterojunctions were prepared via a method involving ultrasonication and calcination. The synthesized photocatalysts were tested and analyzed via various testing techniques, and their hydrogen evolution rates were evaluated. Compared with pure ZIS, ZIS/CFO with different mass ratios of CFO to ZIS showed improved photocatalytic hydrogen production performance, and the optimal photoactivity showed a nearly 12-fold increase, which can be attributed to the formation of p-n junctions and the formed internal electric field, accelerating the separation of electron-hole pairs and effectively improving the photocatalytic hydrogen evolution rate. The excellent stability of the ZIS/CFO composite was proven by three cycle experiments. In addition, the ZIS/CFO composite also possessed excellent magnetic properties to realize facial magnetic recoverability. This work paves the way for the design and preparation of magnetically recoverable p-n heterojunction photocatalysts.

Star-shaped porous nitrogen-doped metal-organic framework carbon as an electrochemical platform for sensitive determination of Cd(II) in environmental and tobacco samples.

In this study, cetyltrimethylammonium bromide and zeolitic imidazolate framework-8 (ZIF-8) were first assembled via the chemical co-precipitation, and high-quality carbon-based metal-free nanomaterials were synthesized using a heat-treatment process. The internal and morphological characteristics of hexagonal Star ZIF-8 were investigated using scanning electron microscopy, X-ray diffraction, and X-ray photoelectron spectroscopy. The electrochemical sensor with a good response to Cd(II) was prepared via square-wave anodic stripping voltammetry (SWASV) with Star ZIF-8 nanomaterial-modified glassy carbon electrodes. The main parameters were adjusted to obtain the optimal stripping response and a wide linear range. Concurrently, under the calculation of SWASV, the sensitivity of Star ZIF-8-Nafion/GCE to Cd(II) was increased by five orders of magnitude (0.5-230 µg/L), and the determination level was even low to 0.48 µg/L. Based on the high anti-interference ability and stability of the sensor, the application potential of Star ZIF-8 carbon-based metal-free nanomaterials for the detection of trace Cd(II) in was confirmed.

Coupling effects of Zn single atom and high curvature supports for improved performance of CO2 reduction.

Single-atom catalysts (SACs) have emerged as one of the most competitive catalysts toward a variety of important electrochemical reactions, thanks to their maximum atom economy, unique electronic and geometric structures. However, the role of SACs supports on the catalytic performance does not receive enough research attentions. Here, we report an efficient route for synthesis of single atom Zn loading on the N-doped carbon nano-onions (ZnN/CNO). ZnN/CNO catalysts show an excellent high selectivity for CO2 electro-reduction to CO with a Faradaic efficiency of CO (FECO) up to 97% at -0.47 V (vs. reversible hydrogen electrode, RHE) and remarkable durability without activity decay. To our knowledge, ZnN/CNO is the best activity for the Zn based catalysts up to now, and superior to single atom Zn loading on the two-dimensional planar and porous structure of graphene substrate, although the graphene with larger surface area. The exact role of such carbon nano-onions (CNO) support is studied systematically by coupling characterizations and electrochemistry with density functional theory (DFT) calculations, which have attributed such good performance to the increased curvature. Such increased curvature modifies the surface charge, which then changes the adsorption energies of key intermediates, and improves the selectivity for CO generation accordingly.

A high-efficiency ammonia-responsive solar evaporator.

The use of solar evaporators, which are capable of purifying water through solar energy, is a potentially attractive solution to relieve the world-wide water shortage problem. However, there may be toxic and volatile substances, such as ammonia, in water bodies, which could be evaporated along with water during the evaporation process, causing contamination of the purified water. In this work, we report an efficient ammonia responsive high-efficiency solar evaporator based on the titanium dioxide nanoparticle (TiO2NP) and polypyrrole nanoparticle (PPyNP) composite. Owing to the synergistic effect between the photo-induced hydrophilicity of the TiO2NPs and the photothermal effect of the PPyNPs, the solar evaporator is able to transport and evaporate water with an efficiency as high as 97.3% and an evaporation rate of 2.9 kg m-2 h-1 (under 2 sun irradiation). Interestingly, due to the ammonia responsiveness, the solar evaporator acts smartly and stops working in the presence of ammonia, thus avoiding the evaporation of this contaminant. In addition, the current solar evaporator is capable of degrading organic pollutants (e.g. dyes), which relies on the photocatalytic activity of TiO2NPs. We thus believe that the ammonia responsive solar evaporator reported in the current study may have great potential in the practical field.

Noble metal-free 0D-1D NiCoP/Mn0.3Cd0.7S nanocomposites for highly efficient photocatalytic H2 evolution under visible-light irradiation.

Efficient and noble metal-free co-catalyst loading is an effective solution for separating and transferring photo-generated carriers and lowering the overpotential in photocatalytic H2 evolution activity. In this work, we designed and prepared a series of novel NiCoP/Mn0.3Cd0.7S (NCP/MCS) composites by modifying MCS nanorods with the co-catalyst NCP using a simple calcination method. Notably, the 10-NCP/MCS composite displays the optimum photocatalytic H2 evolution rate of 118.5 mmol g-1 h-1 under visible-light irradiation. This is approximately 3.39 times higher than that of pure MCS. The corresponding apparent quantum efficiency is 10.2% at 420 nm. The superior photocatalytic activity of the NCP/MCS composites can be attributed to the efficient separation of photogenerated carriers caused by the intimate heterojunction interface between NCP and MCS, smaller transfer resistance, and lower overpotential of NCP. Moreover, the NCP/MCS composites exhibit remarkable photostability. A plausible mechanism is proposed.

Low-Cost, Robust Pressure-Responsive Smart Windows with Dynamic Switchable Transmittance.

Mechanically responsive smart windows with adjustable light transmittance have attracted more and more attention due to their great potential in our daily life. However, their fabrication normally requires complicated preparation such as oxygen plasma treatment and high-cost materials (i.e., poly(dimethylsiloxane) (PDMS)), which hinders their practical applications. Herein, a principally different mechanically responsive smart window, i.e., a pressure-responsive smart window, is reported, which is achieved by harnessing the synergistic interactions (i.e., hydrogen bonding and surface roughness compensation) between the two constituent parts, i.e., hydrogel and agar films. The pressure-responsive smart window features the ultrafast response time (37.5 ms) and high transmittance changes (∼50%) with excellent repeatability, which can be stained with different colors and operated on a flexible substrate. Since the pressure-responsive smart window enables the utilization of the low-cost material and does not require the external energy input, it is anticipated that it may have great potential in practical applications.

A selective and sensitive fluorescent probe for bilirubin in human serum based on europium(III) post-functionalized Zr(IV)-Based MOFs.

In the present study, a kind of Eu(III) post-functionalized Zr(IV)-based metal-organic framework (UiO-66(COOH)2, Zr-MOF: Eu3+) was synthesized and utilized as an independently luminescent probe for sensing bilirubin (BR) in human serum, a biomarker of jaundice hepatitis. It can be served as a turn-off fluorescent switch for BR because its red emission from Eu3+ can be easily quenched by BR through a fluorescent resonant energy transfer (FRET) process between BR and its ligands, and as a result, BR is recognized successfully. Particularly, Zr-MOF: Eu3+ has shown many appealing properties, such as high sensitivity, quick response (less than 1 min), broad response window (0-15 µM), and excellent selectivity. Most importantly, a kind of portable test paper based on Zr-MOF: Eu3+ probe has been developed for directly assessing the level of BR in real human serum and further diagnosing bilirubin-related diseases via visually observing the luminescent color variation.

Visible-Light-Driven Water-Fueled Ecofriendly Micromotors Based on Iron Phthalocyanine for Highly Efficient Organic Pollutant Degradation.

The light-driven micromotor has been demonstrated to have great potential in the environmental remediation field. However, it is still challenging to develop highly efficient, ecofriendly, and visible-light-powered micromotors for organic pollutant degradation. In this paper, we report an ecofriendly micromotor based on iron phthalocyanine (FePc) and gelatin, which exhibits the visible-light-driven self-propulsion behavior using water fuel based on the photocatalytic reaction and self-diffusiophoresis mechanism. Fast motion behavior is observed which induces the rapid agitation of the solution. This, together with the excellent photocatalytic activity, makes the FePc-based micromotor highly efficient when utilized in the degradation of organic pollutants with a normalized reaction rate constant of 2.49 × 10-2 L m-2 s-1, which is by far the fastest and is far superior than the stationary counterpart. The external fuel-free propulsion and the high efficiency in pollutant degradation make the current micromotor potentially attractive for environmental remediation.