Interconnected Periodic Macroporous NaNbO3 for High-Efficiency Solar-Driven Photocatalytic Hydrogen Evolution.

Highly ordered periodic macroporous structures have been extensively utilized to significantly enhance the photocatalytic activity. However, constructing 3D interconnected ordered porous ternary nanostructures with highly crystalline frameworks remains a formidable challenge. Here, we introduce the design and fabrication of 3D interconnected periodic macroporous NaNbO3 (PM NaNbO3) to effectively increase the density of surface-active sites and optimize the photogenerated carrier-transfer efficiency. By incorporating Pt as a cocatalyst, PM NaNbO3 exhibits an exceptional photocatalytic hydrogen generation rate of 10.04 mmol h-1 g-1, which is approximately six and five times higher than those of calcined NaNbO3 (C-NaNbO3) and hydrothermal NaNbO3 (H-NaNbO3), respectively. This outstanding performance can be attributed to the synergistic effects arising from its well-interconnected pore architecture, large surface area, enhanced light absorption capability, and improved charge carrier separation and transport efficiency. The findings presented in this study demonstrate an innovative approach toward designing hierarchically periodic macroporous materials for solar-driven hydrogen production.

Coupling Reliable Interfacial Carrier Migration Channels with Visible-Light Response Antennas in ZnO-Based Heterostructure for Ameliorated Photocatalytic Hydrogen Generation.

Engineering targeted and reliable charge transfer pathways in multiphase photocatalysts remains a challenge. Herein, we conceptualize the Cd@CdS-ZnO/reduced graphene oxide (rGO)/ZnS heterostructures coupled with reliable carrier migration channels and visible-light response antennas by building rGO-integrated electrochemical nanoreactors and an ion-exchange process. In this ternary catalyst, the Cd clusters and rGO perform as charge relays to boost carrier transport via the Z-scheme route and accelerate photogenerated carriers to react with surface-adsorbed substances. Meanwhile, thanks to CdS, the heterostructures have photocatalytic properties under visible light illumination and can also inhibit self-corrosion by shielding Cd clusters to avoid disrupting charge transfer channels. Therefore, the special heterostructure demonstrates fascinating photocatalytic hydrogen production activity without the intervention of cocatalysts. This work provides a feasible protocol for improving the interfaces between metals and semiconductors to achieve efficient photocatalytic hydrogen generation.

Catalytic CO Oxidation on the Cu+-Ov-Ce3+ Interface Constructed by an Electrospinning Method for Enhanced CO Adsorption at Low Temperature.

It is crucial to eliminate CO emissions using non-noble catalysts. Cu-based catalysts have been widely applied in CO oxidation, but their activity and stability at low temperatures are still challenging. This study reports the preparation and application of an efficient copper-doped ceria electrospun fiber catalyst prepared by a facile electrospinning method. The obtained 10Cu-Ce fiber catalyst achieved complete CO oxidation at a temperature as low as 90 °C. However, a reference 10Cu/Ce catalyst prepared by the impregnation method needed 110 °C to achieve complete CO oxidation under identical reaction conditions. Asymmetric oxygen vacancies (ASOV) at the interface between copper and cerium were constructed, to effectively absorb gas molecules involved in the reaction, leading to the enhanced oxidation of CO. The exceptional ability of the 10Cu-Ce catalyst to adsorb CO is attributed to its unique structure and surface interaction phase Cu+-Ov-Ce3+, as demonstrated by a series of characterizations and DFT calculations. This novel approach of using electrospinning offers a promising technique for developing low-temperature and non-noble metal-based catalysts.

Hierarchically Periodic Macroporous Niobium Oxide Architecture for Enhanced Hydrogen Evolution.

The fabrication of periodic macroporous (PM) in Nb2O5 via morphological control is crucial for improving the photocatalytic hydrogen evolution efficiency. In this study, Nb2O5 with PM is synthesized using a straightforward colloidal crystal templating approach. This material features an open, interconnected macroporous architecture with nanoscale walls, high crystallinity, and substantial porosity. Extensive characterization reveals that this hierarchically structured Nb2O5 possesses abundant surface active sites and is capable of capturing light effectively, facilitating rapid mass transfer and diffusion of reactants and markedly suppressing the recombination of photoexcited charge carriers. Macroporous Nb2O5 exhibits superior water-splitting hydrogen evolution performance compared with its bulk and commercial counterparts, achieving a hydrogen production rate of 405 µmol g-1 h-1, surpassing that of bulk Nb2O5 (B-Nb2O5) and commercial Nb2O5 (C-Nb2O5) by factors of 5 and 33, respectively. This study proposes an innovative strategy for the design of hierarchically structured PM, thereby significantly advancing the hydrogen evolution potential of Nb2O5.

Precise Tuning of Bilayer Ultrasmall MoS2 Featuring Inhibition of Carrier Recombination and Fast Surface Chemistry for Green H2 Evolution.

Achieving water splitting to produce green H2 , using the noble-metal-free MoS2 , has attracted huge interest from researchers. However, tuning the number of MoS2 layers precisely while obtaining small lateral sizes to surge the H2 -evolution rate is a tremendous challenge. Here, a bottom-up strategy is designed for the in situ growth of ultrasmall lateral-sized MoS2 with tunable layers on CdS nanorods (CN) by controlling the decomposition temperature and concentration of substrate seed (NH4 )2 MoS4 . Here, the bilayer MoS2 and CN coupling (2L-MoS2 /CN) exhibits the optimum photocatalytic activity. Compared to thicker MoS2 , the 2L-MoS2 has sufficient reduction capacity to drive photocatalytic H2 evolution and the ultrasmall lateral size provides more active sites. Meanwhile, the indirect bandgap, in contrast to the direct bandgap of the monolayer MoS2 , suppresses the carrier recombination transferred to 2L-MoS2 . Under the synergistic effect of both, 2L-MoS2 /CN has fast surface chemical reactions, resulting in the photocatalytic H2 -evolution rate of up to 41.86 mmol g-1 h-1 . A novel strategy is provided here for tuning the MoS2 layers to achieve efficient H2 evolution.

Boosting Low-Temperature CO2 Hydrogenation over Ni-based Catalysts by Tuning Strong Metal-Support Interactions.

Rational design of low-cost and efficient transition-metal catalysts for low-temperature CO2 activation is significant and poses great challenges. Herein, a strategy via regulating the local electron density of active sites is developed to boost CO2 methanation that normally requires >350 °C for commercial Ni catalysts. An optimal Ni/ZrO2 catalyst affords an excellent low-temperature performance hitherto, with a CO2 conversion of 84.0 %, CH4 selectivity of 98.6 % even at 230 °C and GHSV of 12,000 mL g-1 h-1 for 106 h, reflecting one of the best CO2 methanation performance to date on Ni-based catalysts. Combined a series of in situ spectroscopic characterization studies reveal that re-constructing monoclinic-ZrO2 supported Ni species with abundant oxygen vacancies can facilitate CO2 activation, owing to the enhanced local electron density of Ni induced by the strong metal-support interactions. These findings might be of great aid for construction of robust catalysts with an enhanced performance for CO2 emission abatement and beyond.

Automatic craniomaxillofacial landmarks detection in CT images of individuals with dentomaxillofacial deformities by a two-stage deep learning model.

BACKGROUND: Accurate cephalometric analysis plays a vital role in the diagnosis and subsequent surgical planning in orthognathic and orthodontics treatment. However, manual digitization of anatomical landmarks in computed tomography (CT) is subject to limitations such as low accuracy, poor repeatability and excessive time consumption. Furthermore, the detection of landmarks has more difficulties on individuals with dentomaxillofacial deformities than normal individuals. Therefore, this study aims to develop a deep learning model to automatically detect landmarks in CT images of patients with dentomaxillofacial deformities. METHODS: Craniomaxillofacial (CMF) CT data of 80 patients with dentomaxillofacial deformities were collected for model development. 77 anatomical landmarks digitized by experienced CMF surgeons in each CT image were set as the ground truth. 3D UX-Net, the cutting-edge medical image segmentation network, was adopted as the backbone of model architecture. Moreover, a new region division pattern for CMF structures was designed as a training strategy to optimize the utilization of computational resources and image resolution. To evaluate the performance of this model, several experiments were conducted to make comparison between the model and manual digitization approach. RESULTS: The training set and the validation set included 58 and 22 samples respectively. The developed model can accurately detect 77 landmarks on bone, soft tissue and teeth with a mean error of 1.81 ± 0.89 mm. Removal of region division before training significantly increased the error of prediction (2.34 ± 1.01 mm). In terms of manual digitization, the inter-observer and intra-observer variations were 1.27 ± 0.70 mm and 1.01 ± 0.74 mm respectively. In all divided regions except Teeth Region (TR), our model demonstrated equivalent performance to experienced CMF surgeons in landmarks detection (p > 0.05). CONCLUSIONS: The developed model demonstrated excellent performance in detecting craniomaxillofacial landmarks when considering manual digitization work of expertise as benchmark. It is also verified that the region division pattern designed in this study remarkably improved the detection accuracy.

Constructing BiOBr1-xIx-y with Abundant Surface Br Vacancies for Excellent Visible-Light Photodegradation Capability of High-Concentration Refractory Contaminants.

Bismuth oxybromide (BiOBr) is a promising photocatalytic semiconductor material due to its unique hierarchical structure and band structure. However, its photocatalytic applications are restricted due to its narrow visible-light absorption range and poor photooxidation capability. In this study, BiOBr1-xIx-y with rich surface Br vacancies (BrVs-rich BiOBr1-xIx-y) was created via a facile indirect substitution strategy. Benefiting from the broadened visible-light response range and reduced recombination rate of photogenerated carriers, BiOBr1-xIx-y shows excellent visible-light photodegradation ability for high-concentration refractory contaminants, such as phenol, tetracycline, bisphenol A, rhodamine B, methyl orange, and even real wastewater. At the same time, the Br vacancies can regulate the band structure of BiOBr1-xIx-y and serve as trap states to promote charge separation, thus facilitating surface photoredox reactions. An in-depth investigation of the Br vacancy effect and photodegradation mechanism was conducted. This novel study revealed the significance of Br vacancies in enhancing the photocatalytic performance of BiOBr under visible light, providing a promising strategy for improving the utilization efficiency of sunlight in wastewater treatment.

In Situ Construction of BiO(ClBr)(1-x)/2Ix-n Solid Solution with Appropriate Surface Iodine Vacancies for Synergistically Boosting Visible-Light Photo-Oxidation Capability.

A proposed BiO(ClBr)(1-x)/2Ix-n solid solution containing abundant iodine vacancies has been constructed through a facile solvothermal treatment strategy. Fascinatingly, the iodine-vacancy BiO(ClBr)(1-x)/2Ix-n solid solution exhibits an outstanding visible-light photocatalytic degradation property for the environmentally hazardous pollutants of methyl orange, tetracycline, and phenol solutions, which is credited to the synergistic effect of iodine vacancies and the solid solution. By manipulating the molar ratios of Cl, Br, and I, the band structure of the solid solution attained is controlled, enabling the samples to maximize the harvest of visible light and to possess strong oxidation features. More importantly, the construction of iodine vacancies is bound to modulate the local surface atomic structure and promotes the efficiency of the separation of photogenerated carriers. Given these, the microstructure and physicochemical and photoelectrochemical properties of the photocatalysts are fully characterized in a series. In addition, the iodine-vacancy BiO(ClBr)(1-x)/2Ix-n solid solution has a stable crystal structure that permits favorable recyclability even after multiple cycles of degradation. This study sheds light on the significance of the simultaneous existence of vacancy and the solid solution for the enhanced performance of photocatalysts and opens up new insights for sustainable solar-chemical energy conversion.

Interfacial elaborating In2O3-decorated ZnO/reduced graphene oxide/ZnS heterostructure with robust internal electric field for efficient solar-driven hydrogen evolution.

Solar-driven hydrogen evolution over ZnO-ZnS heterostructures is considered as a promising strategy for sustainable-energy issues. However, the industrialization of this strategy is still constrained by suppressed carrier migration, rapid charge recombination, and the inevitable utilization of noble-metal particles. Herein, we envision a novel strategy of successfully introducing In2O3 into the ZnO-ZnS heterostructure. Benefiting from the optimized internal electric field and the charge carrier migration mode based on the direct Z-scheme, the interfacial elaborating In2O3-decorated ZnO/reduced graphene oxide (rGO)/ZnS heterostructure manifests smooth charge migration, suppressed electron-hole pair recombination, and increased surface active sites. More importantly, the in situ introduction of In2O3 optimizes the construction of the internal electric field, favoring directional light-triggered carrier migration. As a result, the light-induced electrons generated from the heterostructure can be efficiently employed for the hydrogen evolution reaction. Hence, this work would shed light on the in situ fabrication of noble-metal-free photocatalysts for solar-driven water splitting.

The Existing Recovery Approaches of the Huangjiu Lees and the Future Prospects: A Mini Review.

Huangjiu lees (HL) is a byproduct in Chinese Huangjiu production with various nutrient and biological functional components. Without efficient treatment, it could cause environmental issues and bioresource wasting. Existing dominant recovery approaches focus on large-scale disposal, but they ignore the application of high-value components. This study discusses the advantages and limitations of existing resourcing approaches, such as feed, food and biogas biological production, considering the efficiency and value of HL resourcing. The extraction of functional components as a suggestion for HL cascade utilization is pointed out. This study is expected to promote the application of HL resourcing.

Improved photoredox activity of the 2D Bi4Ti3O12-BiVO4-Bi4V2O10 heterostructure via the piezoelectricity-enhanced charge transfer effect.

Introducing piezoelectric materials with the built-in electric field caused by mechanical force has been confirmed as an effective strategy to boost the separation efficiency of photoexcited charge carriers that determines the photocatalytic performance. In this study, we introduced Bi4Ti3O12 with superior piezoelectric properties into BiVO4-Bi4V2O10 materials to synthesize a 2D Bi4Ti3O12-BiVO4-Bi4V2O10 photocatalyst via a facile hydrothermal method. Compared with bare BiVO4, the Bi4Ti3O12-BiVO4-Bi4V2O10 piezo-photocatalytic activity towards Cr(VI) removal and oxygen evolution is boosted remarkably under both illumination and ultrasound treatments. The promoted photocatalytic activity can be ascribed to the accelerated photoexcited carrier separation efficiency driven by the polarization electric field and the synergy effect in the heterostructure. This work provides a simple and sustainable strategy for the design and development of piezo-photocatalysts with high photoredox activity capacity.

Robust poly(3,4-ethylenedioxythiophene) granules loaded Cu/Ni-doped Pd catalysts for high-efficiency electrooxidation of ethylene glycol.

In our work, poly(3,4-ethylenedioxythiophene) (PEDOT) granules supported Cu/Ni-doped Pd electrocatalysts (PdCu/PEDOT and PdNi/PEDOT) were synthesized for ethylene glycol (EG) oxidation in alkaline medium. The amorphous PEDOT granules as the catalyst supports provide plenty of attachment sites for PdCu and PdNi nanoparticles. The optimized Pd1Cu3/PEDOT and Pd7Ni3/PEDOT catalysts both perform superior mass-based activity, area-based activity and intrinsic activity for EG oxidation as compared to other control samples. Moreover, chronoamperometry and long-term cyclic voltammetry tests demonstrate that the Pd1Cu3/PEDOT catalyst performs optimal anti-poisoning capability and catalytic durability. The outstanding electrocatalytic performance can be attributed to the favourable dispersion of Pd1Cu3 and Pd7Ni3 nanoparticles on the PEDOT granules and the synergistic effects between Pd, Cu/Ni atoms and the electron-rich conjugated structure of PEDOT. In summary, this work synthesized two Pd/PEDOT-based electrocatalysts with promising catalytic application prospect in direct ethylene glycol fuel cell (DEGFC), which may provide some theoretical support for the design and synthesis of competent electrocatalysts for DEGFC.

Interface Engineering of a 2D/2D BiVO4/Bi4V2O10 Heterostructure with Improved Photocatalytic Photoredox Activity.

Bismuth vanadate (BiVO4) is a promising photocatalyst for water pollution degradation and photocatalytic oxygen evolution. In this work, we prepared 2D/2D BiVO4-Bi4V2O10 heterostructure with tight interfacial contact via a facile one-step hydrothermal process. The crystal structure and morphology of the samples could be easily regulated by changing the pH values of the solution. The BiVO4-Bi4V2O10 heterostructure exhibited an enhanced photodegradation rate of Cr(VI) and oxygen evolution that of bare BiVO4, indicating that the synergistic effect and the interfacial fusions between BiVO4 and Bi4V2O10 can effectively promote the migration and separation rate of photoexcited charge carriers.

Indirect Substitution Constructing Halogen-Vacancy BiOCl1-xIn Solid Solution with a Suitable Surface Structure for Enhanced Photoredox Performance.

Photocatalytic technology has made a series of breakthroughs in environmental remediation, but the degradation performance of persistent heavy metal ions and organic pollutants is not particularly excellent. In addition, the layered structure of bismuth oxyhalides (BiOX, X = I, Br, and Cl) has been a popular material for photodegradation and photoelectrochemistry. Accordingly, with a view to construct a suitable band structure and control the surface structure, it is necessary to develop a strategy to synthesize a BiOCl1-xIn solid solution with halogen vacancies. In this study, halogen vacancies are in situ introduced into the BiOCl1-xIn solid solution through constructing chemical bonds between the hydroxyl groups in glycerol and the I ions during the growth process. The band of the halogen-vacancy BiOCl1-xIn solid solution is widened and active sites centered at halogen vacancies are formed in the direction favorable for the photocatalytic reaction, resulting in enhanced performance in the reduction of Cr(VI) and the oxidation of phenol. The results obtained can provide a new idea for the design of efficient photocatalysts by controlling the formation of halogen vacancies.

Adsorption of Transition-Metal Clusters on Graphene and N-Doped Graphene: A DFT Study.

Using the dispersion-corrected density functional theory (DFT-D3) method, we systematically studied the adsorption of 15 kinds of transition-metal (TM) clusters on pristine graphene (Gr) and N-doped graphene (N-Gr). It has been found that TMn (n = 1-4) clusters adsorbed on the N-Gr surface are much stronger than those on the pristine Gr surface, while 3d series clusters present similar geometries on Gr and N-Gr surfaces. The most preferred sites of TMs migrate from hollow to bridge to the top site on the Gr surface along the d series in the periodic table, while the preferred sites of TMs migrate in a much more complex manner on the N-Gr surface. It has also been found that charge transfer decreases along the d series for adsorbed clusters on both surfaces, but adsorbed clusters present less charge transfer on the N-Gr surface than on the Gr surface. What is more interesting is that some TM (Tc, Ru, and Re) clusters change the growth mechanism from the three-dimensional (3D) growth mode on the Gr surface to the two-dimensional (2D) growth mode on the N-Gr surface. At last, it has been found that adsorbed clusters are more dispersed on the N-Gr surface than on the pristine Gr surface due to growth and average aggregation energies.

Cadmium Sulfide 3D Photonic Crystal with Hierarchically Ordered Macropores for Highly Efficient Photocatalytic Hydrogen Generation.

Cadmium sulfide is a potential candidate for photocatalytic water splitting. However, CdS nanoparticles have a high recombination rate of photoinduced carriers induced by aggregation. Therefore, decreasing the recombination rate and increasing the migration rate of photogenerated carriers are essential to drive the development and application of CdS in hydrogen production. In this study, we design CdS with a three-dimensional ordered macroporous (3DOM) structure using polymethylmethacrylate as a template. It not only retains the excellent visible light response of CdS but also improves the easy recombination of photogenerated carriers in CdS nanoparticles by taking advantage of the unique ability of mass transfer, charge separation, and migration in the 3DOM structure. Meanwhile, the highly ordered periodic structure of 3DOM CdS can produce a slow photon effect of photonic crystals to obtain more photoinduced carriers. In particular, we found that a suitable stop-band position is beneficial to maximize the utilization of the slow photon effect. The photocatalytic hydrogen evolution rate of Pt-CdS is considerably improved after constructing the 3DOM structure. This study provides a new design strategy of ordered macroporous sulfide catalysts to achieve high photocatalytic activity.

Three-dimensionally ordered Macroporous perovskite sodium tantalum for robust hydrogen and hydrogen peroxide production.

Constructing photocatalytic materials into three-dimensionally ordered macroporous (3DOM) is considered an effective strategy for improving mass transfer behaviors and shortening the electron migration path. However, this strategy is challenging for ternary semiconductors because they cannot be directly synthesized by traditional thermal decomposition methods. Ternary systems need to face the structural instability caused by the construction of macroporous morphology, which limits the application of the ordered macroporous structure. In this work, we designed a novel and efficient two-step crystal nucleation strategy for constructing a highly stable ternary ordered macroporous structure. Here, 3DOM NaTaO3 was reported as a promising candidate. Compared with nonporous NaTaO3, which has no catalytic activity in pure water, 807.9 and 280.1 µmol g-1h-1 of H2 and H2O2 production rates were first achieved on the 3DOM NaTaO3. Furthermore, the rate of photocatalytic H2 evolution over the 3DOM NaTaO3 improved sharply to 3.9 mmol g-1h-1 in methanol aqueous solution, which was 139 times that of nonporous NaTaO3. The construction of 3DOM NaTaO3 enables the participation of the bulk interior in photochemical reaction and provides more options for later decoration. This work opens a new door for constructing more 3DOM ternary semiconductors for catalytic reactions.

Ecological wetland paradigm drives water source improvement in the stream network of Yangtze River Delta.

Jiaxing created a precedent using bypass riparian marshes to purify micro-polluted water sources in China. Pond-wetland complex with constructed root channel technology becomes a paradigm which can be analogized as "human-body wetland model" based on bionics or biomimetics. Heterogeneous plant-bed/ditch system with highly active land/water ecotone interfaces, especially meandering boundaries, breeds many biochemical reactions "living areas". Optimization of hydraulic regulation promotes redox environment alternations and wetland treatment efficiency. Here we reported a series of upgrades and performances in Guanjinggang wetland after the Shijiuyang prototype. Morphological reform of plant-bed/ditch system played a vital role. Spatially root channel zone was main force of wetland purification, and temporally the treatment effect was higher in low-temperature seasons indicating non-temperature dependent mechanisms worked. Water pollution comprehensive index improved steadily from IV to III, and comprehensive pollution load was reduced by ca. 40%-60%. Comprehensive evaluation function value further showed the gradients purification effect of the upgraded wetland. Ecological wetlands ameliorated source water quality, and reduced drinking water treatment reagents, thereby bringing about economic benefits. Through wetlands operation, people can see how the micro-polluted surface water becomes clear and clean, so promoting a significant social benefit. As a viable component of urban green space, wetlands could beautify regional eco-environment, freshen the air, increase urban ecological taste, and enhance the eco-environmental protection publicity. Thus, the multifunctional service values and indirect benefits are substantial. Jiaxing ecological wetlands provide a typical paradigm for water pollution remediation in developing countries and plays a leading role in technology engineering radiation effect.

[Removal of Oxytetracycline from Water Using Blast Furnace Slag Loaded Sulfide Nanoscale Zero-valent Iron].

Blast furnace slag loaded with sulfide nano zero valent iron (S-nZVI@BFS) was applied to remove oxytetracycline (OTC) from water. S-nZVI@BFS was synthesized via liquid reduction and characterized using scanning electron microscopy (SEM), X-ray diffraction (XRD), and Brunauer, Emmett and Teller (BET) theory. The effect of reaction time, initial concentration of OTC, initial pH, and coexisting hexavalent chromium[Cr(Ⅵ)] were investigated. The results show that Fe and S were successfully immobilized on the surface of S-nZVI@BFS, the specific surface area and pore volume of which increased to 141.986 m2·g-1 and 0.388 cm3·g-1, respectively, following the loading of nZVI and sulfurization. The utilization rate of the surface active sites of S-nZVI@BFS was improved with an increase of the initial concentration of OTC; the removal rate increased from 20.12 mg·g-1 to 202.74 mg·g-1 when the initial concentration of OTC was increased from 10 mg·L-1 to 100 mg·L-1. The removal rate decreased with pH, declining from 99.78 mg·g-1 to 41.12 mg·g-1 when pH was increased from 3 to 11 due to the switch from Fendon oxidation to electrostatic adsorption. There was notable competition between OTC and Cr(Ⅵ) meaning that Cr(Ⅵ) can inhibit the removal of OTC, which is dose dependent.