Defect-Induced All-Solid-State Frustrated Lewis Pair on Metal-Organic Monolayer Accelerating Photocatalytic CO2 Reduction with H2O Vapor.

Understanding the structure-performance relationships of a frustrated Lewis pair (FLP) at the atomic level is key to yielding high efficiency in activating chemically "inert" molecules into value-added products. A sound strategy was developed herein through incorporating oxygen defects into a Zr-based metal-organic layer (Zr-MOL-D) and employing Lewis basic proximal surface hydroxyls for the in situ formation of solid heterogeneous FLP (Zr4-δ-VO-Zr-OH). Zr-MOL-D exhibits a superior CO2 to CO conversion rate of 49.4 µmol g-1 h-1 in water vapor without any sacrificing agent or photosensitizer, which is about 12 times higher than that of pure MOL (Zr-MOL-P), with extreme stability even after being placed for half a year. Theoretical and experimental results reveal that the introduction of FLP converts the process of the crucial intermediate COOH* from an endothermic reaction to an exothermic spontaneous reaction. This work is expected to provide new prospects for developing efficient MOL-based photocatalysts in FLP chemistry through a sound defect-engineering strategy.

Defective Biphenylene as High-Efficiency Hydrogen Evolution Catalysts.

Electrocatalysts play a pivotal role in advancing the application of water splitting for hydrogen production. This research unveils the potential of defective biphenylenes as high-efficiency catalysts for the hydrogen evolution reaction. Using first-principles simulations, we systematically investigated the structure, stability, and catalytic performance of defective biphenylenes. Our findings unveil that defect engineering significantly enhances the electrocatalytic activity for hydrogen evolution. Specifically, biphenylene with a double-vacancy defect exhibits an outstanding Gibbs free energy of -0.08 eV, surpassing that of Pt, accompanied by a remarkable exchange current density of -3.08 A cm-2, also surpassing that of Pt. Furthermore, we find the preference for the Volmer-Heyrovsky mechanism in the hydrogen evolution reaction, with a low energy barrier of 0.80 eV. This research provides a promising avenue for developing novel metal-free electrocatalysts for water splitting with earth-abundant carbon elements, making a significant step toward sustainable hydrogen production.

The Influence of Heat Treatment Temperature on Tensile Properties of Metal-Bonded Diamond Composites Fabricated via Selective Laser Melting.

Selective Laser Melting (SLM) is an effective technology for fabricating new types of porous metal-bonded diamond tools with complex geometries. However, due to the high cooling rate and internal stresses during SLM fabrication, defects such as high porosities and interface gaps still need to be resolved before it can be considered for use in other applications. The influence of heat treatment temperature on internal characterization, interface microstructures, and tensile properties of AlSi7Mg-bonded diamond composites fabricated by SLM were investigated in this work. From experimental results, the porosities of HT-200, HT-350, and HT-500 specimens were 12.19%, 11.37%, and 11.14%, respectively, showing a slightly lower percentage than that of the No-HT specimen (13.34%). Here, HT represents "Heat Treatment". For No-HT specimens, an obvious un-bonding area can be seen in the interface between AlSi7Mg and diamond, whereas a relative closer interface can be observed for HT-500 specimens. After heat treatment, the elastic modulus of specimens showed a relative stable value (16.77 ± 2.79~18.23 ± 1.72 GPa), while the value of yield strength decreased from 97.24 ± 4.48 to 44.94 ± 7.06 MPa and the value of elongation increased from 1.98 ± 0.05 to 6.62 ± 0.51%. This difference can be attributed mainly to the disappearance of the solid-solution hardening effect due to the increase of Si content after heat treatment.

Densification of SiCp/Al-Fe-V-Si Composites by the Wedge Rolling Method.

The densification of a SiCp/Al-Fe-V-Si billet was achieved by reducing the pores and oxide film between the particles by rolling. The wedge pressing method was used to improve the formability of the composite after jet deposition. The key parameters, mechanisms, and laws of wedge compaction were studied. The results showed that the pass rate was reduced by 10 to 15 percent when using steel molds during the wedge pressing process if the distance between the two ends of the billet was about 10 mm, which was beneficial to improve the compactness and formability of the billet. The density and stress of the surface of the material were higher than those of the interior, where the distribution of density and stress tended to be uniform as the overall volume of the material shrank. During the wedge extrusion process, the material in the preforming area was thinned along the thickness direction, while the material in the main deformation area was lengthened along the length direction. Under plane strain conditions, the wedge formation of spray-deposited composites follows the plastic deformation mechanism of porous metals. The true relative density of the sheet was higher than the calculated value during the initial stamping phase, but was lower than the calculated value when the true strain exceeded 0.55. This was due to the accumulation and fragmentation of SiC particles, which made the pores difficult to remove.

Rich Indium-Vacancies In2 S3 with Atomic p-n Homojunction for Boosting Photocatalytic Multifunctional Properties.

Design and development of highly efficient photocatalytic materials are key to employ photocatalytic technology as a sound solution to energy and environment related challenges. This work aims to significantly boost photocatalytic activity through rich indium vacancies (VIn ) In2 S3 with atomic p-n homojunction through a one-pot preparation strategy. Positron annihilation spectroscopy and electron paramagnetic resonance reveal existence of VIn in the prepared photocatalysts. Mott-Schottky plots and surface photovoltage spectra prove rich VIn In2 S3 can form atomic p-n homojunction. It is validated that p-n homojunction can effectively separate carriers combined with photoelectrochemical tests. VIn decreases carrier transport activation energy (CTAE) from 0.64 eV of VIn -poor In2 S3 to 0.44 eV of VIn -rich In2 S3 . The special structure endows defective In2 S3 with multifunctional photocatalysis properties, i.e., hydrogen production (872.7 µmol g-1 h-1 ), degradation of methyl orange (20 min, 97%), and reduction in heavy metal ions Cr(VI) (30 min, 98%) under simulated sunlight, which outperforms a variety of existing In2 S3 composite catalysts. Therefore, such a compositional strategy and mechanistic study are expected to offer new insights for designing highly efficient photocatalysts through defect engineering.

Quantitative Evaluation of Carrier Dynamics in Full-Spectrum Responsive Metallic ZnIn2S4 with Indium Vacancies for Boosting Photocatalytic CO2 Reduction.

The influence of defects on quantitative carrier dynamics is still unclear. Therefore, full-spectrum responsive metallic ZnIn2S4 (VIn-rich-ZIS) rich in indium vacancies and exhibiting high CO2 photoreduction efficiency was synthesized for the first time. The influence of the defects on the carrier dynamic parameters was studied quantitatively; the results showed that the minority carrier diffusion length (LD) is closely related to the catalytic performance. In situ infrared spectroscopy and theoretical calculations revealed that the presence of indium vacancies lowers the energy barrier for CO2 to CO conversion via the COOH* intermediate. Hence, the high rate of CO evolution reaches 298.0 µmol g-1 h-1, a nearly 28-fold enhancement over that with ZnIn2S4 (VIn-poor-ZIS), which is not rich in indium vacancies. This work fills the gaps between the catalytic performance of defective photocatalysts and their carrier dynamics and may offer valuable insight for understanding the mechanism of photocatalysis and designing more efficient defective photocatalysts.

Visible-Light-Responsive UiO-66(Zr) with Defects Efficiently Promoting Photocatalytic CO2 Reduction.

It is of great importance to understand the relationship between the structure and properties at the atomic level, which provides a solid platform for the design of efficient heterogeneous catalysts. However, it remains a challenge to elucidate the roles of the structure of reaction sites in the catalytic activity of active sites due to the lack of understanding of the structure of specific active site species. Herein, taking the metal-organic framework (MOF) UiO-66(Zr) as a prototype, MOF catalysts with all-solid-state frustrated Lewis pairs (FLPs) Zr3+-OH were synthesized in situ by adding acetic acid (HAc) as a modulator. By introducing missing linkers, UiO-66(Zr) first becomes a visible-light-responsive photocatalyst for CO2 reduction. The in situ Fourier transform infrared (FTIR) spectrum reveals that b-CO32- is the key intermediate for the activation of CO2 molecules through FLPs Zr3+-OH. Moreover, defective UiO-66(Zr) could "self-breath" by surface hydroxyls. This finding not only provides a new avenue for utilizing UV-responsive MOFs by defect engineering but also sheds light on its catalytic activity at the atomic level.

Critical Aspects of Metal-Organic Framework-Based Materials for Solar-Driven CO2 Reduction into Valuable Fuels.

Photoreduction of CO2 into value-added fuels is one of the most promising strategies for tackling the energy crisis and mitigating the "greenhouse effect." Recently, metal-organic frameworks (MOFs) have been widely investigated in the field of CO2 photoreduction owing to their high CO2 uptake and adjustable functional groups. The fundamental factors and state-of-the-art advancements in MOFs for photocatalytic CO2 reduction are summarized from the critical perspectives of light absorption, carrier dynamics, adsorption/activation, and reaction on the surface of photocatalysts, which are the three main critical aspects for CO2 photoreduction and determine the overall photocatalytic efficiency. In view of the merits of porous materials, recent progress of three other types of porous materials are also briefly summarized, namely zeolite-based, covalent-organic frameworks based (COFs-based), and porous semiconductor or organic polymer based photocatalysts. The remarkable performance of these porous materials for solar-driven CO2 reduction systems is highlighted. Finally, challenges and opportunities of porous materials for photocatalytic CO2 reduction are presented, aiming to provide a new viewpoint for improving the overall photocatalytic CO2 reduction efficiency with porous materials.

A stable nanoscaled Zr-MOF for the detection of toxic mycotoxin through a pH-modulated ratiometric luminescent switch.

A stable nanoscaled single-excitation ratiometric luminescent pH sensor (MPDB-PCN) over a broad pH range from 2.5 to 8.6 is fabricated through post-synthetic modification of PCN-224 with naphthalimide-derived molecules. Due to the rapid, sensitive and linear response to pH, MPDB-PCN is capable of detecting 3-nitropropionic acid (3-NPA), an acid neurotoxin in food safety, with a low detection limit of 15 µM in sugarcane juice.

Upregulated expression of SAC3D1 is associated with progression in gastric cancer.

SAC3 domain containing 1 (SAC3D1) has been reported to be involved in numerous types of cancer. However, the role of SAC3D1 in GC has not yet been elucidated. In the present study, the mRNA expression level of SAC3D1 between GC and normal tissues were assessed with a continuous variable meta­analysis based on multiple datasets from public databases. The protein expression level of SAC3D1 in GC and normal tissues was assessed by an in­house immunohistochemistry (IHC). The association between SAC3D1 expression and some clinical parameters was assessed based on the TCGA and IHC data. Survival analysis was performed to assess the association between SAC3D1 expression and the survival of GC patients. The co­expressed genes of SAC3D1 were determined by integrating three online tools, and the enrichment analyses were performed to determine SAC3D1­related pathways and hub co­expressed genes. SAC3D1 was significantly upregulated in GC tumor tissues in comparison to normal tissues with the SMD being 0.45 (0.12, 0.79). The IHC results also indicated that SAC3D1 protein expression in GC tissues was markedly higher than in normal tissues. The SMD following the addition of the IHC data was 0.59 (0.11, 1.07). The protein levels of SAC3D1 were positively associated with the histological grade, T stage and N stage of GC (P<0.001). The TCGA data also revealed that the SAC3D1 mRNA level was significantly associated with the N stage (P<0.001). Moreover, prognosis analysis indicated that SAC3D1 was closely associated with the prognosis of patients with GC. Moreover, 410 co­expressed genes of SAC3D1 were determined, and these genes were mainly enriched in the cell cycle. In total, 4 genes (CDK1, CCNB1, CCNB2 and CDC20) were considered key co­expressed genes. On the whole, these findings demonstrate that SAC3D1 is highly expressed in GC and may be associated with the progression of GC.

Microstructure and Properties of Thermal Electrode Material Si3N4⁻MoSi2 Composite Ceramics.

With good high temperature and corrosive resistance performance, ceramic based composites can be used as promising materials to replace metal thermocouple materials. In this study, Si3N4⁻MoSi2 composites were prepared via hot pressing technology. X-ray diffraction (XRD), optical microscopy (OM), and scanning electron microscopy (SEM) were used to analyze the microstructure of the composites. The mechanical properties and electrical conductivity were tested. The results showed that the composites were composed of β-Si3N4, MoSi2, a small amount of Mo5Si3, and an amorphous glassy phase. The MoSi2 phase was evenly distributed in the matrix. The percolation network was formed with increasing MoSi2 content. The strength of the composites reached its maximum value when the MoSi2 content reached a critical point. The electrical conductivity behaved like a typical percolation phenomenon. The percolation threshold was about 30% to 45%.

Expression, purification and characterization of a novel recombinant SVTLE, r-agkihpin-2, from Gloydius halys Pallas venom gland in Escherichia coli.

In our previous work, a thrombin-like enzyme (TLE), agkihpin, was successfully isolated, purified, cloned and named from the venom of Gloydius halys Pallas, having fibrinolytic, fibrinogenolytic and thrombosis-reduced activities, attenuating migration of liver cancer cell, and without bleeding risk. To explore the possibility of agkihpin as a thrombolytic and/or anti-metastasis agent in the future, in this study recombinant agkihpin was expressed and purified in Escherichia coli, and its biological activities investigated. Thus, r-agkihpin-2 was successfully expressed and purified and confirmed by Western blot and peptide mass fingerprinting. After purification and renaturation, 46 mg (399 U) of active r-agkihpin-2 was obtained from 1 L bacterial culture. The results of the arginine esterase activity assay, fibrin plate test fibrinogenolytic activity assay, thrombin-induced venous thrombosis assay, Scratch-Wound assay and bleeding assay showed that active r-agkihpin-2 had slightly lower TAME hydrolytic, fibrinolytic, fibrinogenolytic, thrombus-reduced and migration-attenuated activities than those of native agkihpin, and had no bleeding risk. These findings confirmed that, active r-agkihpin-2 could be further investigated for thrombolytic and/or anti-metastasis drug discovery in the future.