Search

Understanding the microstructure of materials and their impact on performance is crucial for new electronic devices design. The strong interaction between multiple degrees of freedom (spin, orbit, charge, and lattice) within perovskite type oxides can generate rich electron phase diagrams. The microscopic modulation of manganese ions electron states in rare earth manganate perovskites is the root of many novel macroscopic quantum behaviors, such as giant magnetoresistance phenomenon. For ABO3 type perovskites, the differences of radii and valence states of A‐site ions are used to regulate the coexistence of B site manganese multivalent states (Mn3+, Mn4+, Mn5+), and its ordered structure in the metastable state will create a new combination of electronic states. The ordered arrangement of the multi‐dimensional space of electronic states can induce unique transport properties. Therefore, the preparation of manganate perovskites will provide strong chemical support to construct new generation quantum devices. This review summarizes the challenges and difficulties on constructing trivalent coexisting metastable phase in manganate perovskites through disproportionation reactions, and discusses the status and potential of designing ideal rectified p‐n junctions taking advantage of this unique structure. Finally, the foregrounds of new quantum states driven by this chemical reaction are prospected. [ABSTRACT FROM AUTHOR]

In natural plants, Mn4CaO5 cluster with metal‐oxo "distorted chair"‐like structure exhibits excellent oxygen evolution activity. However, the performance of biomimetic oxygen evolution catalysts based on the Mn4CaO5‐like structure is far inferior to expectations. Herein, Ca and Ni are first doped together into birnessite and constructed a "distorted chair"‐like structure unit Mn4‐xNixCaO5 in a birnessite‐like Ca‐Mn(Ni)‐O catalyst, the biomimetic Mn4‐xNixCaO5 unit efficiently activates lattice oxygen and boosts the O─O coupling in oxygen evolution reaction (OER), which allows the catalyst to perform superior OER activity with an outstanding overpotential of 184 mV at 300 mA cm−2. Besides, the birnessite‐like Ca‐Mn(Ni)‐O catalyst is stabilized by coupling to NiMnO3 nanoplate, thus forming a stable catalyst that can work for >500 h without attenuation. This work optimizes biomimetic structures by introducing new elements, which provides new insight into developing efficient biomimetic materials. [ABSTRACT FROM AUTHOR]

Electrocatalytic CO2 reduction reaction (CO2RR) in acidic media is a promising approach to overcome the unavoidable formation of carbonates in alkaline or neutral electrolytes. However, the proton-rich environment near the catalyst surface favors hydrogen evolution reactions (HER), leading to lower energy efficiency of the desired products, especially in industrial-level current densities. Here, quaternary ammonium cationic surfactant (cetyltrimethylammonium bromide (CTAB)) was introduced into acidic electrolyte to modulate the interfacial microenvironment, which greatly enhanced CO2 electroreduction to formic acid (HCOOH) at the Bi/C nanoparticles electrode. Using a Bi/C nanoparticles electrode with CTAB added, constant production of formic acid was enabled with a cathodic energy efficiency of > 40% and maximum FEHCOOH (FE = Faradaic efficiency) of 86.2% at −400 mA·cm−2 over 24 h. Combined with in-situ attenuated total reflection Fourier transform infrared spectroscopy, the concentration of *OCHO intermediates significantly increased after CTAB modification, confirming that the hydrophobic interface microenvironment formed by dynamic adsorption of positively charged long alkyl chains on Bi/C nanoparticle electrodes inhibited HER and improved the selectivity of CO2RR to HCOOH. [ABSTRACT FROM AUTHOR]

Metal-organic frameworks (MOFs) have shown significant potential as photocatalysts. It has been widely assumed that all catalytic active sites within MOFs are functional in photocatalytic reactions but for a three-dimensional MOF, whether the internal catalytic active sites can effectively absorb light and actively contribute to photocatalytic reactions remains to be explored. In this context, we synthesized a two-dimensional nanosheet MOF (2D-MOF) and a three-dimensional bulk MOF (3D-MOF) composed of Zr6 clusters and tetracarboxylic porphyrin (TCPP) by the approach described in the literature. Re(bpy)(CO)3Cl (bpy = 2,2′-bipyridine), which has remarkable CO2 photoreduction ability, was introduced to the two MOFs to create two new photocatalysts 2D-MOF-Re and 3D-MOF-Re, respectively. Photocatalytic CO2 reduction experiments show that based on the equal number of catalytic active sites, the CO turnover number (TON) of 2D-MOF-Re reaches 27.8 in 6 h, which is 50 times that of 3D-MOF-Re. The result shows that certain catalytic active sites inside the bulk MOF are inactive due to the inability to absorb light. This study illuminates the potential of the dimensional reduction approach in the design of photocatalysts to exploit the capabilities fully. [ABSTRACT FROM AUTHOR]

Two-dimensional (2D) covalent organic frameworks (COFs) and their derivatives have been widely applied as electrocatalysts owing to their unique nanoscale pore configurations, stable periodic structures, abundant coordination sites and high surface area. This work aims to construct a non-thermodynamically stable Pt-N2 coordination active site by electrochemically modifying platinum (Pt) single atoms into a fully conjugated 2D COF as conductive agent-free and pyrolysis-free electrocatalyst for the hydrogen evolution reaction (HER). In addition to maximizing atomic utilization, single-atom catalysts with definite structures can be used to investigate catalytic mechanisms and structure-activity relationships. In this work, in-situ characterizations and theoretical calculations reveal that a nitrogen-rich graphene analogue COF not only exhibits a favorable metal-support effect for Pt, adjusting the binding energy between Pt sites to H* intermediates by forming unique Pt-N2 instead of the typical Pt-N4 coordination environment, but also enhances electron transport ability and structural stability, showing both conductivity and stability in acidic environments. In addition to maximizing atomic utilization, single-atom catalysts with defined structures can be used to investigate catalytic mechanisms and structure-activity relationships. Here, authors study a non-thermodynamically stable Pt-N2 active site for the electrochemical hydrogen evolution reaction. [ABSTRACT FROM AUTHOR]

Two-dimensional (2D) covalent organic frameworks (COFs) and their derivatives have been widely applied as electrocatalysts owing to their unique nanoscale pore configurations, stable periodic structures, abundant coordination sites and high surface area. This work aims to construct a non-thermodynamically stable Pt-N2 coordination active site by electrochemically modifying platinum (Pt) single atoms into a fully conjugated 2D COF as conductive agent-free and pyrolysis-free electrocatalyst for the hydrogen evolution reaction (HER). In addition to maximizing atomic utilization, single-atom catalysts with definite structures can be used to investigate catalytic mechanisms and structure-activity relationships. In this work, in-situ characterizations and theoretical calculations reveal that a nitrogen-rich graphene analogue COF not only exhibits a favorable metal-support effect for Pt, adjusting the binding energy between Pt sites to H* intermediates by forming unique Pt-N2 instead of the typical Pt-N4 coordination environment, but also enhances electron transport ability and structural stability, showing both conductivity and stability in acidic environments. In addition to maximizing atomic utilization, single-atom catalysts with defined structures can be used to investigate catalytic mechanisms and structure-activity relationships. Here, authors study a non-thermodynamically stable Pt-N2 active site for the electrochemical hydrogen evolution reaction. [ABSTRACT FROM AUTHOR]

Solar-light-driven CO2 reduction CO to CH4 and C2H6 is a complex process involving multiple elementary reactions and energy barriers. Therefore, achieving high CH4 activity and selectivity remains a significant challenge. Here, we integrate bifunctional Cu2O and Cu-MOF (MOF = metal-organic framework) core–shell co-catalysts (Cu2O@Cu-MOF) with semiconductor TiO2. Experiments and theoretical calculations demonstrate that Cu2O (Cu+ facilitates charge separation) and Cu-MOF (Cu2+ improves the CO2 adsorption and activation) in the core–shell structure have a synergistic effect on photocatalytic CO2 reduction, reducing the formation barrier of the key intermediate ⋆COOH and ⋆CHO. The photocatalyst exhibits high CH4 yield (366.0 µmol·g−1·h−1), efficient electron transfer (3283 µmol·g−1·h−1) and hydrocarbon selectivity (95.5%), which represents the highest activity of Cu-MOF-based catalysts in photocatalytic CO2 reduction reaction. This work provides a strategy for designing efficient photocatalysts from the perspective of precise regulation of components. [ABSTRACT FROM AUTHOR]

The growth and sustainable development of humanity is heavily dependent upon molecular nitrogen (N2) fixation. Herein we discover ambient catalyst-free disproportionation of N2 by water plasma which occurs via the distinctive HONH-HNOH+• intermediate to yield economically valuable nitroxyl (HNO) and hydroxylamine (NH2OH) products. Calculations suggest that the reaction is prompted by the coordination of electronically excited N2 with water dimer radical cation, (H2O)2+•, in its two-center-three-electron configuration. The reaction products are collected in a 76-needle array discharge reactor with product yields of 1.14 μg cm–2 h–1 for NH2OH and 0.37 μg cm–2 h–1 for HNO. Potential applications of these compounds are demonstrated to make ammonia (for NH2OH), as well as to chemically react and convert cysteine, and serve as a neuroprotective agent (for HNO). The conversion of N2 into HNO and NH2OH by water plasma could offer great profitability and reduction of polluting emissions, thus giving an entirely look and perspectives to the problem of green N2 fixation. The growth and sustainable development of humanity is heavily dependent upon N2 fixation. Herein, authors developed an ambient catalyst-free disproportionation of N2 by water plasma to yield economically valuable nitroxyl and hydroxylamine products. [ABSTRACT FROM AUTHOR]

The design of high-entropy oxides (HEOs) with specific morphologies and tunable compositions is of great significance for the development of efficient electrocatalysts for the oxygen evolution reaction (OER). Herein, a series of two-dimensional HEOs with abundant active sites are prepared by a self-sacrificing template method via rapid Joule heating. Among them, high-entropy oxide (FeCoNiMoRu)3O4 exhibits outstanding OER performance with low overpotential (199 mV@10 mA cm—2, 266 mV@100 mA cm—2), small Tafel slope (40 mV dec—1), and excellent long-term stability (operating at 500 mA cm—2 for 100 hours without significant decay). The perfect performance of (FeCoNiMoRu)3O4 can be attributed to the large active surface area generated by the nanosheet structure, shortened ion transport pathway, entropy stabilization mechanism and multi-element synergism. Therefore, the two-dimensional high-entropy oxide prepared by using a carbon sacrificial template is expected to be a promising candidate material for industrial water splitting. [ABSTRACT FROM AUTHOR]

The shuttle effect of polysulfides poses a significant obstacle to the commercialization of lithium-sulfur (Li–S) batteries. Covalent organic frameworks have been widely used in Li–S batteries as porous crystalline materials to suppress the shuttle effect. Herein, a 3,5-bis(trifluoromethyl)benzyl (BTFMB-TzDa) modified triazine-based covalent organic framework was synthesized. The high electronegativity and large steric hindrance of the BTFMB-TzDa modified separator successfully suppressed the diffusion of polysulfides, leading to improved capacity and cyclic stability of Li–S batteries. Cells with the BTFMB-TzDa modified separator exhibited a high initial capacity of 1205 mA h g−1 at 0.2C and 657 mA h g−1 at 3.0C. Furthermore, the capacity still remained at 501 mA h g−1 after 500 cycles. The BTFMB-TzDa modified separator provides an alternative strategy for the construction of high-performance Li–S batteries. [ABSTRACT FROM AUTHOR]

Background: Classical swine fever and porcine reproductive and respiratory syndrome have seriously affected the development of the swine breeding industry in China. Vaccine immunization remains the main way to prevent these infections. The aim of this study was to establish an optimized protocol for vaccine immunization against classical swine fever virus (CSFV) and porcine reproductive and respiratory syndrome virus (PRRSV). Methods: Blood samples were collected from the anterior vena cava of pigs after immunization, and blood indices, secreted levels of specific antibodies and neutralizing antibodies associated with humoral immunity, the proliferation capacity of T lymphocytes as a measure of cellular immunity, and secreted levels of IFN-γ and TNF-α were determined. Results: The results showed that simultaneous immunization against CSFV and PRRSV infections induced strong and specific humoral and T-cellular immune responses, high levels of cytokine IFN-γ secretion and delayed secretion of cytokine TNF-α. Moreover, significantly higher lymphocyte percentages and red blood cell and leukocyte counts were found in the group simultaneously immunized against CSFV and PRRSV. However, no statistically significant differences were observed in hemoglobin values, neutrophil counts, and median cell percentages among the S + PRRS, PRRS-S, and S-PRRS groups. Conclusion: This study demonstrated that simultaneous immunization against CSFV and PRRSV had the advantages of inducing a rapid, enhanced, and long-lasting immune response. These findings provide a theoretical basis for the establishment of a reasonable and optimized vaccine immunization protocol against CSFV and PRRSV in combination with a variety of other vaccine inoculations. [ABSTRACT FROM AUTHOR]

Metal single atoms (SAs) anchored in carbon support via coordinating with N atoms are efficient active sites to oxygen reduction reaction (ORR). However, rational design of single atom catalysts with highly exposed active sites is challenging and urgently desirable. Herein, an anion exchange strategy is presented to fabricate Fe‐N4 moieties anchored in hierarchical carbon nanoplates composed of hollow carbon spheres (Fe‐SA/N‐HCS). With the coordinating O atoms are substituted by N atoms, Fe SAs with Fe‐O4 configuration are transformed into the ones with Fe‐N4 configuration during the thermal activation process. Insights into the evolution of central atoms demonstrate that the SAs with specific coordination environment can be obtained by modulating in situ anion exchange process. The strategy produces a large quantity of electrochemical accessible site and high utilization rate of Fe‐N4. Fe‐SA/N‐HCS shows excellent ORR electrocatalytic performance with half‐wave potential of 0.91 V (vs. RHE) in 0.1 M KOH, and outstanding performance when used in rechargeable aqueous and flexible Zn‐air batteries. The evolution pathway for SAs demonstrated in this work offers a novel strategy to design SACs with various coordination environment and enhanced electrocatalytic activity. [ABSTRACT FROM AUTHOR]

Metal single atoms (SAs) anchored in carbon support via coordinating with N atoms are efficient active sites to oxygen reduction reaction (ORR). However, rational design of single atom catalysts with highly exposed active sites is challenging and urgently desirable. Herein, an anion exchange strategy is presented to fabricate Fe‐N4 moieties anchored in hierarchical carbon nanoplates composed of hollow carbon spheres (Fe‐SA/N‐HCS). With the coordinating O atoms are substituted by N atoms, Fe SAs with Fe‐O4 configuration are transformed into the ones with Fe‐N4 configuration during the thermal activation process. Insights into the evolution of central atoms demonstrate that the SAs with specific coordination environment can be obtained by modulating in situ anion exchange process. The strategy produces a large quantity of electrochemical accessible site and high utilization rate of Fe‐N4. Fe‐SA/N‐HCS shows excellent ORR electrocatalytic performance with half‐wave potential of 0.91 V (vs. RHE) in 0.1 M KOH, and outstanding performance when used in rechargeable aqueous and flexible Zn‐air batteries. The evolution pathway for SAs demonstrated in this work offers a novel strategy to design SACs with various coordination environment and enhanced electrocatalytic activity. [ABSTRACT FROM AUTHOR]

Moderate eg filling for octahedral metal cations (MOh) is strongly correlated with the electrocatalytic water oxidation performance in the oxides system. Here, the eg fillings of NiOh and FeOh in NiFe2O4‐based spinel are controllably regulated by introducing an external radical of catalytically inactive MoSx as an electron acceptor via a novel ultrasonic anchored pyrolysis strategy. The electron occupied in eg orbit of MOh emigrates with the amount of MoS hanging on the apical of octahedral sites, and results in a salutary transition from high to medium eg occupancy state, as confirmed by the X‐ray absorption spectroscopy and X‐ray photoelectron spectroscopy. In addition, benefiting from the abundant unsaturated S atoms in amorphous MoSx, the MOh at the surface furthest activates and consequently shows a superior water oxidation performance. Density functional theory also reveals that the eg fillings of Ni and Fe decrease to 1.4 and 1.2 after MoSx modification, which can effectively reduce the free energy of the OOH* intermediates in the oxygen evolution reaction process. This work opens an avenue for further releasing the electrocatalytic activity of octahedral sites through bridging external phases with rational electron‐capturing/donating capability. [ABSTRACT FROM AUTHOR]

Manganese-based cathode materials are promising candidates for aqueous zinc ion batteries (AZIBs) by reason of their low cost and high energy density. However, their practical applicability is hampered by the intrinsic defects of poor electrical conductivity, sluggish reaction kinetics, and severe structural deterioration. Herein, we constructed a hierarchically porous structure composed of carbon-encapsulated MnO nanoparticles (MOC) and three-dimensional (3D) nitrogen-doped graphene aerogel (NGA) (denoted as MOC@NGA). The hybrid was synthesized by a facile in-situ coprecipitation and annealing of manganese-based metal-organic framework (Mn-MOF74) and NGA composite (Mn-MOF74@NGA). Specifically, the carbon shells inherited from organic ligand of Mn-MOF74 could restrain the volume changes of MnO, and the porous NGA prevented the agglomeration of MOC nanoparticles and enriched the types of interfacial chemical bonds. Profiting from the synergistic effect of rich interface chemical bonds and dual-carbon protection, the MOC@NGA hybrids exhibit fast interfacial electron/charge transfer and transport, and outstanding structural stability. Therefore, MOC@NGA cathode delivers an excellent rate performance (270 and 99.8 mAh g −1 at 0.1 and 2.0 A g−1) and maintains an excellent specific capacity of 151.6 mAh g −1 after 2,000 cycles at 1.0 A g−1. Moreover, the fabricated MOC@NGA-based quasi-solid-state battery not only achieves outstanding flexibility but also displays impressive cycling stability, demonstrating a promising potential for portable and flexible equipment. This work provides a feasible strategy for the fabrication of the bridging structure of manganese-based oxides and porous carbon matrix for high-specific capacity and durable AZIBs cathodes. [ABSTRACT FROM AUTHOR]

Oxygen vacancies‐enriched black TiO2 is one promising support for enhancing hydrogen evolution reaction (HER). Herein, oxygen vacancies enriched black TiO2 supported sub‐nanometer Pt clusters (Pt/TiO2‐OV) with metal support interactions is designed through solvent‐free microwave and following low‐temperature electroless approach for the first time. High‐temperature and strong reductants are not required and then can avoid the aggregation of decorated Pt species. Experimental and theoretical calculation verify that the created oxygen vacancies and Pt clusters exhibit synergistic effects for optimizing the reaction kinetics. Based on it, Pt/TiO2‐OV presents remarkable electrocatalytic performance with 18 mV to achieve 10 mA cm−2 coupled with small Tafel slope of 12 mV dec−1. This work provides quick synthetic strategy for preparing black titanium dioxide based nanomaterials. [ABSTRACT FROM AUTHOR]

Oxygen vacancies‐enriched black TiO2 is one promising support for enhancing hydrogen evolution reaction (HER). Herein, oxygen vacancies enriched black TiO2 supported sub‐nanometer Pt clusters (Pt/TiO2‐OV) with metal support interactions is designed through solvent‐free microwave and following low‐temperature electroless approach for the first time. High‐temperature and strong reductants are not required and then can avoid the aggregation of decorated Pt species. Experimental and theoretical calculation verify that the created oxygen vacancies and Pt clusters exhibit synergistic effects for optimizing the reaction kinetics. Based on it, Pt/TiO2‐OV presents remarkable electrocatalytic performance with 18 mV to achieve 10 mA cm−2 coupled with small Tafel slope of 12 mV dec−1. This work provides quick synthetic strategy for preparing black titanium dioxide based nanomaterials. [ABSTRACT FROM AUTHOR]

Background: Classical swine fever and porcine reproductive and respiratory syndrome have seriously affected the development of the swine breeding industry in China. Vaccine immunization remains the main way to prevent these infections. The aim of this study was to establish an optimized protocol for vaccine immunization against classical swine fever virus (CSFV) and porcine reproductive and respiratory syndrome virus (PRRSV). Methods: Blood samples were collected from the anterior vena cava of pigs after immunization, and blood indices, secreted levels of specific antibodies and neutralizing antibodies associated with humoral immunity, the proliferation capacity of T lymphocytes as a measure of cellular immunity, and secreted levels of IFN-γ and TNF-α were determined. Results: The results showed that simultaneous immunization against CSFV and PRRSV infections induced strong and specific humoral and T-cellular immune responses, high levels of cytokine IFN-γ secretion and delayed secretion of cytokine TNF-α. Moreover, significantly higher lymphocyte percentages and red blood cell and leukocyte counts were found in the group simultaneously immunized against CSFV and PRRSV. However, no statistically significant differences were observed in hemoglobin values, neutrophil counts, and median cell percentages among the S + PRRS, PRRS-S, and S-PRRS groups. Conclusion: This study demonstrated that simultaneous immunization against CSFV and PRRSV had the advantages of inducing a rapid, enhanced, and long-lasting immune response. These findings provide a theoretical basis for the establishment of a reasonable and optimized vaccine immunization protocol against CSFV and PRRSV in combination with a variety of other vaccine inoculations. [ABSTRACT FROM AUTHOR]

Identification of novel drugs for anti-African swine fever (ASF) applications is of utmost urgency, as it negatively affects pig farming and no effective vaccine or treatment is currently available. African swine fever virus (ASFV) encoded pS273R is a cysteine protease that plays an important role in virus replication. E64, acting as an inhibitor of cysteine protease, has been established as exerting an inhibitory effect on pS273R. In order to obtain a better understanding of the interaction between E64 and pS273R, common docking, restriction docking, and covalent docking were employed to analyze the optimal bonding position between pS273R−E64 and its bonding strength. Additionally, three sets of 100 ns molecular dynamics simulations were conducted to examine the conformational dynamics of pS273R and the dynamic interaction of pS273R−E64, based on a variety of analytical methods including root mean square deviation (RMSD), root mean square fluctuation (RMSF), free energy of ligand (FEL), principal component analysis (PCA), and molecular mechanics/Poisson–Boltzmann surface area (MM/PBSA) analysis. The results show that E64 and pS273R exhibited close binding degrees at the activity center of ASFV pS273R protease. The data of these simulations indicate that binding of E64 to pS273R results in a reduction in flexibility, particularly in the ARM region, and a change in the conformational space of pS273R. Additionally, the ability of E64 to interact with polar amino acids such as ASN158, SER192, and GLN229, as well as charged amino acids such as LYS167 and HIS168, seems to be an important factor in its inhibitory effect. Finally, Octet biostratigraphy confirmed the binding of E64 and pS273R with a KD value of 903 uM. Overall, these findings could potentially be utilized in the development of novel inhibitors of pS273R to address the challenges posed by ASFV. [ABSTRACT FROM AUTHOR]

Background: Classical swine fever and porcine reproductive and respiratory syndrome have seriously affected the development of the swine breeding industry in China. Vaccine immunization remains the main way to prevent these infections. The aim of this study was to establish an optimized protocol for vaccine immunization against classical swine fever virus (CSFV) and porcine reproductive and respiratory syndrome virus (PRRSV). Methods: Blood samples were collected from the anterior vena cava of pigs after immunization, and blood indices, secreted levels of specific antibodies and neutralizing antibodies associated with humoral immunity, the proliferation capacity of T lymphocytes as a measure of cellular immunity, and secreted levels of IFN-γ and TNF-α were determined. Results: The results showed that simultaneous immunization against CSFV and PRRSV infections induced strong and specific humoral and T-cellular immune responses, high levels of cytokine IFN-γ secretion and delayed secretion of cytokine TNF-α. Moreover, significantly higher lymphocyte percentages and red blood cell and leukocyte counts were found in the group simultaneously immunized against CSFV and PRRSV. However, no statistically significant differences were observed in hemoglobin values, neutrophil counts, and median cell percentages among the S + PRRS, PRRS-S, and S-PRRS groups. Conclusion: This study demonstrated that simultaneous immunization against CSFV and PRRSV had the advantages of inducing a rapid, enhanced, and long-lasting immune response. These findings provide a theoretical basis for the establishment of a reasonable and optimized vaccine immunization protocol against CSFV and PRRSV in combination with a variety of other vaccine inoculations. [ABSTRACT FROM AUTHOR]

The African Swine Fever virus (ASFV) causes an infectious viral disease in pigs of all ages. The development of antiviral drugs primarily aimed at inhibition of proteases required for the proteolysis of viral polyproteins. In this study, the conformation of the pS273R protease in physiological states were investigated, virtually screened the multi-protein conformation of pS273R target proteins, combined various molecular docking scoring functions, and identified five potential drugs from the Food and Drug Administration drug library that may inhibit pS273R. Subsequent validation of the dynamic interactions of pS273R with the five putative inhibitors was achieved using molecular dynamics simulations and binding free energy calculations using the molecular mechanics/Poison-Boltzmann (Generalized Born) (MM/PB(GB)SA) surface area. These findings demonstrate that the arm domain and Thr159-Lys167 loop region of pS273R are significantly more flexible compared to the core structural domain, and the Thr159-Lys167 loop region can serve as a "gatekeeper" in the substrate channel. Leucovorin, Carboprost, Protirelin, Flavin Mononucleotide, and Lovastatin Acid all have Gibbs binding free energies with pS273R that were less than −20 Kcal/mol according to the MM/PBSA analyses. In contrast to pS273R in the free energy landscape, the inhibitor and drug complexes of pS273R showed distinct structural group distributions. These five drugs may be used as potential inhibitors of pS273R and may serve as future drug candidates for treating ASFV. [ABSTRACT FROM AUTHOR]

Herein, we designed selectively doped Co3O4 to explore the effect of coordination sites, in which the octahedral and tetrahedral sites were modulated by simple doping with ions of different radiuses (Al and In). Compared to octahedral regulation, the synergistic regulation of both tetrahedral sites and octahedral sites can induce a higher intrinsic activity, which is because they possess improved electrical conductivity and facilitate the formation of highly active Co3+/Co4+ species during the oxygen evolution reaction (OER). [ABSTRACT FROM AUTHOR]

Cobalt-plasma sparked by a pulsed laser was utilized for the first time to modify a BiVO4 photoanode, inducing surface structural reconstruction and CoOx/BiVO4 composite construction. Combining charge redistribution and cobalt, the center of hole accumulation and catalytic activity, the photoanode with optimized charge transfer capacity exhibits a 3 times improvement in photoelectrochemical water oxidation performance. [ABSTRACT FROM AUTHOR]

The electronic structure of composites plays a critical role in photocatalytic conversion, whereas it is challenging to modulate the orbital for an efficient catalyst. Herein, we regulated the t2g orbital occupancy state of Ti to realize efficient CO2 conversion by adjusting the amount of photo‐deposited Cu in the Cu/TiO2 composite. For the optimal sample, considerable electrons transfer from the Cu d orbital to the Ti t2g orbital, as proven by X‐ray absorption spectroscopy. The Raman spectra results also corroborate the electron enrichment on the Ti t2g orbital. Further theoretical calculations suggested that the orbital energy of the Ti 3d orbital in TiO2 is declined, contributing to accepting Cu 3d electrons. As a result, the Cu/TiO2 composite exhibited an extremely high selectivity of 95.9 % for CO, and the productivity was 15.27 μmol g−1 h−1, which is almost 6 times that of the original TiO2. Our work provides a strategy for designing efficient photocatalysis as a function of orbital regulation. [ABSTRACT FROM AUTHOR]

The electronic structure of composites plays a critical role in photocatalytic conversion, whereas it is challenging to modulate the orbital for an efficient catalyst. Herein, we regulated the t2g orbital occupancy state of Ti to realize efficient CO2 conversion by adjusting the amount of photo‐deposited Cu in the Cu/TiO2 composite. For the optimal sample, considerable electrons transfer from the Cu d orbital to the Ti t2g orbital, as proven by X‐ray absorption spectroscopy. The Raman spectra results also corroborate the electron enrichment on the Ti t2g orbital. Further theoretical calculations suggested that the orbital energy of the Ti 3d orbital in TiO2 is declined, contributing to accepting Cu 3d electrons. As a result, the Cu/TiO2 composite exhibited an extremely high selectivity of 95.9 % for CO, and the productivity was 15.27 μmol g−1 h−1, which is almost 6 times that of the original TiO2. Our work provides a strategy for designing efficient photocatalysis as a function of orbital regulation. [ABSTRACT FROM AUTHOR]

Constructing a high-efficiency composite material for CO2 photoreduction is a key step to the achievement of carbon neutralization, but a comprehensive understanding of the factors that dictate CO2 reduction activity remains elusive. Here, we constructed a series of Cu in situ combined on Cu2O (Cu/Cu2O-1, -2, -3) via an acid disproportionation method with various processing time. The optimal photocatalyst (Cu/Cu2O-2) affords CO at a rate of 10.43 µmol·g−1·h−1, which is more than fourfold to that of pristine Cu2O. Electron transfer in the samples was detected by X-ray absorption spectroscopy (XAS) as well as X-ray photoelectron spectroscopy (XPS). Interestingly, the best photoreduction performance was not achieved by the sample possessing the most electron transfer (Cu/Cu2O-1) but by the one with moderate electron transfer (Cu/Cu2O-2). By virtue of density functional theory (DFT) calculations, a linear relationship between Bader charge variation (Δq) of the active sites and adsorption energy of CO2 reduction intermediates was discovered, wherein the moderate charge transfer corresponds to appropriate adsorption energy, which benefits CO2 photoreduction activity substantially. This work provides guidance for the construction of composite catalysts for efficient CO2 photoreduction in a perspective of the quantity of electron transfer. [ABSTRACT FROM AUTHOR]

Proton exchange membrane water electrolysis (PEMWE) is currently developed for the design of mature industrial‐scale manufactures with commercialization. It needs reducing hydrogen production cost by lowering material cost and increasing operating current density. In engineering perspectives, the study of electrolytic performance during dynamic operation is crucial for PEMWE system management and process control. However, there is few multiphysics models of PEMWE considering transient behavior. The one‐dimensional (1D) comprehensive dynamic multiphysics model allows to explore temporal transport phenomena in the PEMWE, and predict electrolytic performance. The 1D model is endorsed by the spatially lumped model from the literature. Changing values of structural and physical properties of porous transport layers (PTLs) and catalyst layers (CLs) allows the observation of their effects on the electrolytic performance and transport phenomena in two‐phase flow regime. It suggests that the appropriate PTL properties, and CL fabrication method can lower the cost and remain high electrolytic performance. [ABSTRACT FROM AUTHOR]

Organic–inorganic hybrid materials hold great promise in commercial energy storage and conversion. This work aims to develop an advanced hybrid material of ultrafine antimony (Sb) nanoparticles uniformly anchored in the pores of COFs (Sb@NGA–CMP) through a facile in situ synthetic strategy. Sb3+ is introduced as an essential catalyst for COF formation and is subsequently fixed in the channels of the COFs by reduction. Such a well-designed architecture affords intimate electron interaction between the Sb nanoparticles and π-conjugated microporous polymers (CMPs) through the nitrogen groups, which greatly accelerates charge transfer along the COF skeleton. Meanwhile, the stable nanostructure of the ultrafine Sb encapsulated in the COFs effectively alleviates the high Sb volume expansion upon long cycling performance. This uniquely designed anode exhibits a high rate performance of 223 mA h g−1 at 5 A g−1 and an excellent sodium storage performance of 344 mA h g−1 after 5000 long cycles at 1 A g−1. Our work provides a promising and facile strategy to construct hybrid organic–inorganic materials for high-performance energy storage applications. [ABSTRACT FROM AUTHOR]

Calcium-ion batteries (CIBs) are considered as promising alternatives in large-scale energy storage due to their divalent electron redox properties, low cost, and high volumetric/gravimetric capacity. However, the high charge density of Ca2+ contributes to strong electrostatic interaction between divalent Ca2+ and hosting lattice, leading to sluggish kinetics and poor rate performance. Here, in situ formed poly(anthraquinonyl sulfide) (PAQS)@CNT composite is reported as nonaqueous calcium-ion battery cathode. The enolization redox chemistry of organics has fast redox kinetics, and the introduction of carbon nanotube (CNT) accelerates electron transportation, which contributes to fast ionic diffusion. As the conductivity of the PAQS is enhanced by the increasing content of CNT, the voltage gap is significantly reduced. The PAQS@CNT electrode exhibits specific capacity (116 mAh g-1 at 0.05 A g-1), high rate capacity (60 mAh g-1 at 4 A g-1), and an initial capacity of 82 mAh g-1 at 1 A g-1 (83% capacity retention after 500 cycles). The electrochemical mechanism is proved to be that the PAQS undergoes reduction reaction of their carbonyl bond during discharge and becomes coordinated by Ca2+ and Ca(TFSI)+ species. Computational simulation also suggests that the construction of Ca2+ and Ca(TFSI)+ co-intercalation in the PAQS is the most reasonable pathway. [ABSTRACT FROM AUTHOR]

Coordination engineering can enhance the activity and stability of the catalyst in heterogeneous catalysis. However, the axial coordination engineering between different groups on the carbon carrier and molecular catalysts in the electrocatalytic carbon dioxide reduction reaction (CO2RR) has been studied rarely. Through coordination engineering strategy, a series of amino (NH2), hydroxyl (OH), and carboxyl (COOH) groups functionalized carbon nanotubes (CNT) immobilized cobalt phthalocyanine (CoPc) catalysts are designed. Compared with no groups, OH groups and COOH groups, NH2 groups can effectively change the coordination environment of the central metal Co, thereby significantly increasing the turnover frequency (TOF) (31.4 s−1 at −0.6 V vs. RHE, CoPc/NH2-CNT > CoPc/OH-CNT > CoPc/COOH-CN > CoPc/CNT). In the flow cell, the CoPc/NH2-CNT catalyst has high carbon monoxide (CO) selectivity at high current density (∼ 100% at −225 mA·cm−2, ∼ 96% at −351 mA·cm−2). Importantly, the CoPc/NH2-CNT catalyst can operate stably for 100 h at 225 mA·cm−2. Theoretical calculations reveal that CoPc/NH2-CNT catalyst is beneficial to the formation of *COOH and desorption of *CO, thus promoting CO2RR. This work provides an excellent platform for understanding the effect of coordination engineering on electrocatalytic performance and promotes a way to explore efficient and stable catalysts in other applications. [ABSTRACT FROM AUTHOR]

Direct ethanol fuel cells are among the most efficient and environmentally friendly energy‐conversion devices and have been widely focused. The ethanol oxidation reaction (EOR) is a multielectron process with slow kinetics. The large amount of by‐product generated by incomplete oxidation greatly reduces the efficiency of energy conversion through the EOR. In this study, a novel type of trimetallene called porous PdWM (M = Nb, Mo and Ta) is synthesized by a facile method. The mass activity (15.6 A mgPd−1) and C1 selectivity (55.5%) of Pd50W27Nb23/C trimetallene, obtained after optimizing the compositions and proportions of porous PdWM, outperform those of commercial Pt/C (1.3 A mgPt−1, 5.9%), Pd/C (5.0 A mgPd−1, 7.2%), and Pd97W3/C bimetallene (9.5 A mgPd−1, 14.1%). The mechanism by which Pd50W27Nb23/C enhances the EOR performance is evaluated by in situ Fourier transform infrared spectroscopy and density functional theory calculations. It is found that W and Nb enhance the adsorption of CH3CH2OH and oxophilic high‐valence Nb accelerates the subsequent oxidation of CO and CHx species. Moreover, Nb promotes the cleavage of CC bonds and increases the C1 selectivity. Pd60W28Mo12/C and Pd64W27Ta9/C trimetallene synthesized by the same method also exhibit excellent EOR performance. [ABSTRACT FROM AUTHOR]

Direct ethanol fuel cells are among the most efficient and environmentally friendly energy‐conversion devices and have been widely focused. The ethanol oxidation reaction (EOR) is a multielectron process with slow kinetics. The large amount of by‐product generated by incomplete oxidation greatly reduces the efficiency of energy conversion through the EOR. In this study, a novel type of trimetallene called porous PdWM (M = Nb, Mo and Ta) is synthesized by a facile method. The mass activity (15.6 A mgPd−1) and C1 selectivity (55.5%) of Pd50W27Nb23/C trimetallene, obtained after optimizing the compositions and proportions of porous PdWM, outperform those of commercial Pt/C (1.3 A mgPt−1, 5.9%), Pd/C (5.0 A mgPd−1, 7.2%), and Pd97W3/C bimetallene (9.5 A mgPd−1, 14.1%). The mechanism by which Pd50W27Nb23/C enhances the EOR performance is evaluated by in situ Fourier transform infrared spectroscopy and density functional theory calculations. It is found that W and Nb enhance the adsorption of CH3CH2OH and oxophilic high‐valence Nb accelerates the subsequent oxidation of CO and CHx species. Moreover, Nb promotes the cleavage of CC bonds and increases the C1 selectivity. Pd60W28Mo12/C and Pd64W27Ta9/C trimetallene synthesized by the same method also exhibit excellent EOR performance. [ABSTRACT FROM AUTHOR]

Chitosan (Cts), a positively charged natural polysaccharide, is employed to functionalize mesoporous titanium dioxide (mTiO2) nanoparticles. The prepared Cts/mTiO2 composite was used as a stationary phase to coat the inner wall of fused‐silica capillary and obtain uniform Cts/mTiO2 film. The Cts/mTiO2 film is applied to detect and enrich phosphopeptides in complex biological samples based on typical in‐tube solid phase microextraction (IT‐SPME) system. This unique Cts/mTiO2 film exhibits excellent enrichment performances of high selectivity (β‐casein and BSA in molar ratio of 1 : 1000), sensitivity (detection limit as low as 40 fmol of β‐casein tryptic digest solution) and high adsorption capacity (124.5 μg mg−1). Meanwhile, the Cts/mTiO2 film possesses preferable reusability and can be reused more than 10 times. These results confirm that the Cts/mTiO2 film possesses potential and satisfactory prospects in phosphoproteomics analysis. [ABSTRACT FROM AUTHOR]

Coordination polymers have received immense attention for proton conduction owing to their highly tunable and designable structures. Herein, based on the flexible ligand 5-(4-pyridine)-methoxyisophthalic acid (H2L), two novel highly chemically stable indium coordination polymers (In-CPs), InL(H2O)Cl·H2O (In–L–Cl) and InL(H2O)(NO3) (In–L–NO3), were synthesized through solvothermal methods. In–L–Cl and In–L–NO3 are isostructural, in which every individual In(III) atom connects to L2− to form a single layer, and coordinated Cl− and NO3− are inserted into the windows of the interlayers. Both of them possess high water and chemical stability. More importantly, the abundant Cl− and NO3− exposed in the interlayer can act as hydrogen bond acceptors to facilitate the formation of a dense hydrogen bonding network, thus improving proton transfer efficiently. Electrochemical impedance spectroscopy shows that In–L–Cl and In–L–NO3 display optimized proton conductivities of 1.88 × 10 −3 and 1.00 × 10 −3 S cm−1 at 100% relative humidity (RH) and 80 °C, respectively. The difference in proton conductivity of In–L–Cl and In–L–NO3 likely stems from the variations in the hydrogen bonding networks formed by lattice water and the different electronegativities of the coordinated anionic functional sites. This study provides an alternative way to prepare highly proton-conductive CPs. [ABSTRACT FROM AUTHOR]

Despite recent advances in targeted therapies and immunotherapies in acute myeloid leukemia, patient prognosis is still dismal given the high frequency of refractory cases or post‐remission relapse. Ferrotherapy, a novel anti‐cancer treatment strategy using iron‐based compounds, can mechanistically bypass the chemoresistance of cancer cells. However, cancer cells often overexpress the transmembrane iron exporter ferroportin that expels accumulated iron into the plasma, which can potentially limit the efficacy of ferrotherapy and lead to systemic toxic effects. Here, a ferro‐therapeutic nanoplatform is designed using fusing hepcidin and leukemia cell‐membrane vesicles on gold nanoparticles (AuNPs)‐loaded hollow mesoporous Prussian Blue (AuPB@LMHep). AuPB@LMHep specifically targeted leukemia cells through ferroportin and is subsequently internalized and disintegrated into iron and AuNPs through autophagy. The accumulation of iron due to blockade of ferroportin‐mediated iron efflux and the depletion of glutathione by the AuNPs triggered ferroptosis. Furthermore, iron accumulation inactivated the endogenous iron‐dependent m6A demethylase, thereby increasing global m6A RNA modification and suppressing multiple oncogenes. Finally, AuPB@LMHep enhanced the immune response to anti‐programmed death ligand1 treatment via increasing cytotoxic tumor‐infiltrating T cells. Pre‐clinical findings provide the proof‐of‐concept of hepcidin‐based nanocomposite as an "epigenetic drug" and immunotherapeutic agent for treating leukemia. [ABSTRACT FROM AUTHOR]

Charge separation and transfer are central issues dominating the underlying energy conversion mechanisms of photosynthetic systems. Here, inspired by nature, a multi‐interfacial engineering strategy for constructing a strongly coupled interactive transmission network for stable and efficient photocatalytic hydrogen production is proposed. A multivariate all‐solid‐state Z‐scheme with intimate electron interactions is formed through strong bridging bonds due to Ti orbit modulation and stacking hybridization between hybrids. The electron couple structure realizes an efficient carrier directional separation and transfer, enabling the charge separation efficiency to be enhanced dramatically by 7.2 times. Furthermore, the resulting material provides a highly stable photocatalytic hydrogen activity, up to 15.29 mmol h−1 g−1, 18.8 times higher than pure carbon nitride, surpassing many reported photocatalysts. This work represents a significant development and helps develop a sound foundation for future design principles in accelerating charge transfer. [ABSTRACT FROM AUTHOR]

Improving proton conductivity and fabricating viable metal‐organic frameworks (MOFs) based proton exchange membranes (PEMs) are central issues exploiting electrolyte MOFs. We aim to design multivariate flexibility synergistic strategy to achieve Flexible MOFs (FMOFs) with high conductivity at a wide range of humidity. In situ powder X‐ray diffraction (PXRD) and temperature‐dependent Fourier transform infrared spectra (FT‐IR) prove the synergistic self‐adaption between dynamic torsion of alkyl sulfonic acid and dynamic breathing of FMOF, forming a continuous hydrogen‐bonding networks to maintain high conductivity. Based on the convincing proton conductivity, we construct a series of long‐term durable MOF‐based PEMs that serve as a bridge between MOF and fuel cell. Consequently, the membrane electrode assembly (MEA) of the flexible PMNS1‐40 exhibits a maximum single‐cell power density of 34.76 mW cm−2 and hopefully opens doors to evaluate the practical application of proton‐conducting MOFs in direct methanol fuel cells. [ABSTRACT FROM AUTHOR]

Improving proton conductivity and fabricating viable metal‐organic frameworks (MOFs) based proton exchange membranes (PEMs) are central issues exploiting electrolyte MOFs. We aim to design multivariate flexibility synergistic strategy to achieve Flexible MOFs (FMOFs) with high conductivity at a wide range of humidity. In situ powder X‐ray diffraction (PXRD) and temperature‐dependent Fourier transform infrared spectra (FT‐IR) prove the synergistic self‐adaption between dynamic torsion of alkyl sulfonic acid and dynamic breathing of FMOF, forming a continuous hydrogen‐bonding networks to maintain high conductivity. Based on the convincing proton conductivity, we construct a series of long‐term durable MOF‐based PEMs that serve as a bridge between MOF and fuel cell. Consequently, the membrane electrode assembly (MEA) of the flexible PMNS1‐40 exhibits a maximum single‐cell power density of 34.76 mW cm−2 and hopefully opens doors to evaluate the practical application of proton‐conducting MOFs in direct methanol fuel cells. [ABSTRACT FROM AUTHOR]