Directional Construction of the Highly Stable Active-Site Ensembles at Sub-2 nm to Enhance Catalytic Activity and Selectivity.

Precise control over the size, species, and breakthrough of the activity-selectivity trade-off are great challenges for sub-nano non-noble metal catalysts. Here, for the first time, a "multiheteroatom induced SMSI + in situ P activation" strategy that enables high stability and effective construction of sub-2 nm metal sites for optimizing selective hydrogenation performance is developed. It is synthesized the smallest metal phosphide clusters (<2 nm) including from unary to ternary non-noble metal systems, accompanied by unprecedented thermal stability. In the proof-of-concept demonstration, further modulation of size and species results in the creation of a sub-2 nm site platform, directionally achieving single atom (Ni1), Ni1+metal cluster (Ni1+Nin), or novel Ni1+metal phosphide cluster synergistic sites (Ni1+Ni2Pn), respectively. Based on thorough structure and mechanism investigation, it is found the Ni1+Ni2Pn site is motivated to achieve electronic structure self-optimizing through synergistic SMSI and site coupling effect. Therefore, it speeds up the substrate adsorption-desorption kinetics in semihydrogenation of alkyne and achieves superior catalytic activity that is 56 times higher than the Ni1 site under mild conditions. Compared to traditional active sites, this may represent the highly effective integration of atom utilization, thermal stability, and favorable site requirements for chemisorption properties and reactivities of substrates.

Tongfu Lifei Decoction Attenuated Sepsis-Related Intestinal Mucosal Injury Through Regulating Th17/Treg Balance and Modulating Gut Microbiota.

Intestinal damage and secondary bacterial translocation are caused by the inflammatory response induced by sepsis. Tongfu Lifei (TLF) decoction has a protective effect on sepsis-related gastrointestinal function injury. However, the relation between gut microbiota, immune barrier, and sepsis under the treatment of TLF have not been well clarified yet. Here, rats were subjected to cecal ligation and puncture (CLP) to create a sepsis model. Subsequently, the TLF decoction was given to CLP rats by gavage, fecal microbiota transplantation (FMT), and antibiotic were used as positive control. TLF suppressed the inflammatory response and improved the pathological changes in the intestines of CLP rats. Besides, TLF promoted the balance of the percentage of the Th17 and Treg cells. Intestinal barrier function was also improved by TLF through enhancing ZO-1, and Occludin and Claudin 1 expression, preventing the secondary translocation of other gut microbiota. TLF dramatically boosted the gut microbiota's alpha- and beta-diversity in CLP rats. Moreover, it increased the relative abundance of anti-inflammatory gut microbiota and changed the progress of the glucose metabolism. In short, TLF regulated the gut microbiota to balance the ratio of Th17/Treg cells, reducing the inflammation in serum and intestinal mucosal injury in rats.

Constructing Asymmetric Charge Polarized NiCo Prussian Blue Analogue for Promoted Electrocatalytic Methanol to Formate Conversion.

The highly selective electrochemical conversion of methanol to formate is of great significance for various clean energy devices, but understanding the structure-to-property relationship remains unclear. Here, the asymmetric charge polarized NiCo prussian blue analogue (NiCo PBA-100) is reported to exhibit remarkable catalytic performance with high current density (210 mA cm-2 @1.65 V vs RHE) and Faraday efficiency (over 90%). Meanwhile, the hybrid water splitting and Zinc-methanol-battery assembled by NiCo PBA-100 display the promoted performance with decent stability. X-ray absorption spectroscopy (XAS) and operando Raman spectroscopy indicate that the asymmetric charge polarization in NiCo PBA leads to more unoccupied states of Ni and occupied states of Co, thereby facilitating the rapid transformation of the high-active catalytic centers. Density functional theory calculations combining operando Fourier transform infrared spectroscopy demonstrate that the final reconstructed catalyst derived by NiCo PBA-100 exhibits rearranged d band properties along with a lowered energy barrier of the rate-determining step and favors the desired formate production.

Intrinsic room-temperature ferromagnetism in a two-dimensional semiconducting metal-organic framework.

The development of two-dimensional (2D) magnetic semiconductors with room-temperature ferromagnetism is a significant challenge in materials science and is important for the development of next-generation spintronic devices. Herein, we demonstrate that a 2D semiconducting antiferromagnetic Cu-MOF can be endowed with intrinsic room-temperature ferromagnetic coupling using a ligand cleavage strategy to regulate the inner magnetic interaction within the Cu dimers. Using the element-selective X-ray magnetic circular dichroism (XMCD) technique, we provide unambiguous evidence for intrinsic ferromagnetism. Exhaustive structural characterizations confirm that the change of magnetic coupling is caused by the increased distance between Cu atoms within a Cu dimer. Theoretical calculations reveal that the ferromagnetic coupling is enhanced with the increased Cu-Cu distance, which depresses the hybridization between 3d orbitals of nearest Cu atoms. Our work provides an effective avenue to design and fabricate MOF-based semiconducting room-temperature ferromagnetic materials and promotes their practical applications in next-generation spintronic devices.

Asymmetric dinitrogen-coordinated nickel single-atomic sites for efficient CO2 electroreduction.

Developing highly efficient, selective and low-overpotential electrocatalysts for carbon dioxide (CO2) reduction is crucial. This study reports an efficient Ni single-atom catalyst coordinated with pyrrolic nitrogen and pyridinic nitrogen for CO2 reduction to carbon monoxide (CO). In flow cell experiments, the catalyst achieves a CO partial current density of 20.1 mA cmgeo-2 at -0.15 V vs. reversible hydrogen electrode (VRHE). It exhibits a high turnover frequency of over 274,000 site-1 h-1 at -1.0 VRHE and maintains high Faradaic efficiency of CO (FECO) exceeding 90% within -0.15 to -0.9 VRHE. Operando synchrotron-based infrared and X-ray absorption spectra, and theoretical calculations reveal that mono CO-adsorbed Ni single sites formed during electrochemical processes contribute to the balance between key intermediates formation and CO desorption, providing insights into the catalyst's origin of catalytic activity. Overall, this work presents a Ni single-atom catalyst with good selectivity and activity for CO2 reduction while shedding light on its underlying mechanism.

Sustainable methane utilization technology via photocatalytic halogenation with alkali halides.

Methyl halides are versatile platform molecules, which have been widely adopted as precursors for producing value-added chemicals and fuels. Despite their high importance, the green and economical synthesis of the methyl halides remains challenging. Here we demonstrate sustainable and efficient photocatalytic methane halogenation for methyl halide production over copper-doped titania using alkali halides as a widely available and noncorrosive halogenation agent. This approach affords a methyl halide production rate of up to 0.61 mmol h-1 m-2 for chloromethane or 1.08 mmol h-1 m-2 for bromomethane with a stability of 28 h, which are further proven transformable to methanol and pharmaceutical intermediates. Furthermore, we demonstrate that such a reaction can also operate solely using seawater and methane as resources, showing its high practicability as general technology for offshore methane exploitation. This work opens an avenue for the sustainable utilization of methane from various resources and toward designated applications.

Analysis of the Contribution of Conformation and Fibrils on Tensile Toughness and Fracture Resistance of Camel Hairs.

Animal hairs, like other natural fibers, display excellent mechanical properties, especially, the tensile toughness and fracture resistance. Several structure-mechanics models have attributed mechanical superiority of hair to its unique nanocomposite structure which consists of intermediate filaments and matrix. However, the contribution of fibrils and their associated interfaces on the mechanical properties of animal hairs remains unclear. Herein, using the small- and wide-angle X-ray scattering, and an ultrahigh-speed microcamera system, it is confirmed that the conformation and fibrils (which represent both nanofibrils and microfibrils) of the keratin channel endow tensile toughness and fracture resistance to camel hairs. During the stretching process, an α-ß transition occurred at the secondary structure level, leading to the formation of a tensile plateau, which improves the toughness compared with the structure without a conformation transition. Meanwhile, fibrils further toughened the camel hairs and resisted their crack propagation through confined fibrillar slippage, splitting, and pulling. These structure-property relations in natural hairs can inspire damage-tolerant polymer fiber design.

VUV-UV-vis photoluminescence, X-ray radioluminescence and energy transfer dynamics of Ce3+ and Eu2+ in Sr2MgSi2O7.

Ce3+ and Eu2+ doped and Ce3+-Eu2+ co-doped Sr2MgSi2O7 phosphors are prepared via a high-temperature solid-state reaction technique. The synchrotron radiation vacuum ultraviolet-ultraviolet (VUV-UV) excitation and ultraviolet-visible (UV-vis) emission spectra of diluted Ce3+ and Eu2+ doped Sr2MgSi2O7 samples are measured at cryogenic temperatures. The electron-vibrational interaction (EVI) between Ce3+ and its surroundings is analyzed. The dependencies of the 4f-5d transitions of Ce3+ on the structure of the host compounds Sr2MgSi2O7, Ba2MgSi2O7 and BaMg2Si2O7 are discussed in detail. Then the thermal quenching channel is proposed based on the measurements of temperature dependent luminescence intensities and decay times of Ce3+ and Eu2+ in Sr2MgSi2O7, and the Ce3+ → Eu2+ energy transfer mechanism is understood by three luminescence dynamic models. In addition, Sr2MgSi2O7:Ce3+/Eu2+ samples are evaluated for the possibilities of X-ray detection applications using X-ray excited luminescence (XEL) spectroscopy, and it was found that they are not suitable.

Operando Direct Observation of Stable Water-Oxidation Intermediates on Ca2-xIrO4 Nanocrystals for Efficient Acidic Oxygen Evolution.

We report Ca2-xIrO4 nanocrystals exhibit record stability of 300 h continuous operation and high iridium mass activity (248 A gIr-1 at 1.5 VRHE) that is about 62 times that of benchmark IrO2. Lattice-resolution images and surface-sensitive spectroscopies demonstrate the Ir-rich surface layer (evolved from one-dimensional connected edge-sharing [IrO6] octahedrons) with high relative content of Ir5+ sites, which is responsible for the high activity and long-term stability. Combining operando infrared spectroscopy with X-ray absorption spectroscopy, we report the first direct observation of key intermediates absorbing at 946 cm-1 (Ir6+═O site) and absorbing at 870 cm-1 (Ir6+OO- site) on iridium-based oxides electrocatalysts, and further discover the Ir6+═O and Ir6+OO- intermediates are stable even just from 1.3 VRHE. Density functional theory calculations indicate the catalytic activity of Ca2IrO4 is enhanced remarkably after surface Ca leaching, and suggest IrOO- and Ir═O intermediates can be stabilized on positive charged active sites of Ir-rich surface layer.

High-performance photocatalytic nonoxidative conversion of methane to ethane and hydrogen by heteroatoms-engineered TiO2.

Nonoxidative coupling of methane (NOCM) is a highly important process to simultaneously produce multicarbons and hydrogen. Although oxide-based photocatalysis opens opportunities for NOCM at mild condition, it suffers from unsatisfying selectivity and durability, due to overoxidation of CH4 with lattice oxygen. Here, we propose a heteroatom engineering strategy for highly active, selective and durable photocatalytic NOCM. Demonstrated by commonly used TiO2 photocatalyst, construction of Pd-O4 in surface reduces contribution of O sites to valence band, overcoming the limitations. In contrast to state of the art, 94.3% selectivity is achieved for C2H6 production at 0.91 mmol g-1 h-1 along with stoichiometric H2 production, approaching the level of thermocatalysis at relatively mild condition. As a benchmark, apparent quantum efficiency reaches 3.05% at 350 nm. Further elemental doping can elevate durability over 24 h by stabilizing lattice oxygen. This work provides new insights for high-performance photocatalytic NOCM by atomic engineering.

Self-adaptive integration of photothermal and radiative cooling for continuous energy harvesting from the sun and outer space.

The sun (∼6,000 K) and outer space (∼3 K) are two significant renewable thermodynamic resources for human beings on Earth. The solar thermal conversion by photothermal (PT) and harvesting the coldness of outer space by radiative cooling (RC) have already attracted tremendous interest. However, most of the PT and RC approaches are static and monofunctional, which can only provide heating or cooling respectively under sunlight or darkness. Herein, a spectrally self-adaptive absorber/emitter (SSA/E) with strong solar absorption and switchable emissivity within the atmospheric window (i.e., 8 to 13 µm) was developed for the dynamic combination of PT and RC, corresponding to continuously efficient energy harvesting from the sun and rejecting energy to the universe. The as-fabricated SSA/E not only can be heated to ∼170 °C above ambient temperature under sunshine but also be cooled to 20 °C below ambient temperature, and thermal modeling captures the high energy harvesting efficiency of the SSA/E, enabling new technological capabilities.

A Defect Engineered Electrocatalyst that Promotes High-Efficiency Urea Synthesis under Ambient Conditions.

Synthesizing urea from nitrate and carbon dioxide through an electrocatalysis approach under ambient conditions is extraordinarily sustainable. However, this approach still lacks electrocatalysts developed with high catalytic efficiencies, which is a key challenge. Here, we report the high-efficiency electrocatalytic synthesis of urea using indium oxyhydroxide with oxygen vacancy defects, which enables selective C-N coupling toward standout electrocatalytic urea synthesis activity. Analysis by operando synchrotron radiation-Fourier transform infrared spectroscopy showcases that *CO2NH2 protonation is the potential-determining step for the overall urea formation process. As such, defect engineering is employed to lower the energy barrier for the protonation of the *CO2NH2 intermediate to accelerate urea synthesis. Consequently, the defect-engineered catalyst delivers a high Faradaic efficiency of 51.0%. In conjunction with an in-depth study on the catalytic mechanism, this design strategy may facilitate the exploration of advanced catalysts for electrochemical urea synthesis and other sustainable applications.

Complementary Operando Spectroscopy identification of in-situ generated metastable charge-asymmetry Cu2-CuN3 clusters for CO2 reduction to ethanol.

Copper-based materials can reliably convert carbon dioxide into multi-carbon products but they suffer from poor activity and product selectivity. The atomic structure-activity relationship of electrocatalysts for the selectivity is controversial due to the lacking of systemic multiple dimensions for operando condition study. Herein, we synthesized high-performance CO2RR catalyst comprising of CuO clusters supported on N-doped carbon nanosheets, which exhibited high C2+ products Faradaic efficiency of 73% including decent ethanol selectivity of 51% with a partial current density of 14.4 mA/cm-2 at -1.1 V vs. RHE. We evidenced catalyst restructuring and tracked the variation of the active states under reaction conditions, presenting the atomic structure-activity relationship of this catalyst. Operando XAS, XANES simulations and Quasi-in-situ XPS analyses identified a reversible potential-dependent transformation from dispersed CuO clusters to Cu2-CuN3 clusters which are the optimal sites. This cluster can't exist without the applied potential. The N-doping dispersed the reduced Cun clusters uniformly and maintained excellent stability and high activity with adjusting the charge distribution between the Cu atoms and N-doped carbon interface. By combining Operando FTIR and DFT calculations, it was recognized that the Cu2-CuN3 clusters displayed charge-asymmetric sites which were intensified by CH3* adsorbing, beneficial to the formation of the high-efficiency asymmetric ethanol.

Synergic Reaction Kinetics over Adjacent Ruthenium Sites for Superb Hydrogen Generation in Alkaline Media.

Ruthenium (Ru)-based electrocatalysts as platinum (Pt) alternatives in catalyzing hydrogen evolution reaction (HER) are promising. However, achieving efficient reaction processes on Ru catalysts is still a challenge, especially in alkaline media. Here, the well-dispersed Ru nanoparticles with adjacent Ru single atoms on carbon substrate (Ru1,n -NC) is demonstrated to be a superb electrocatalyst for alkaline HER. The obtained Ru1,n -NC exhibits ultralow overpotential (14.8 mV) and high turnover frequency (1.25 H2  s-1 at -0.025 V vs reversible hydrogen electrode), much better than the commercial 40 wt.% Pt/C. The analyses reveal that Ru nanoparticles and single sites can promote each other to deliver electrons to the carbon substrate. Eventually, the electronic regulations bring accelerated water dissociation and reduced energy barriers of hydroxide/hydrogen desorption on adjacent Ru sites, then an optimized reaction kinetics for Ru1,n -NC is obtained to achieve superb hydrogen generation in alkaline media. This work provides a new insight into the catalyst design in simultaneous optimizations of the elementary steps to obtain ideal HER performance in alkaline media.

Design of a Sub-6 GHz Dielectric Resonator Antenna with Novel Temperature-Stabilized (Sm1-xBix)NbO4 (x = 0-0.15) Microwave Dielectric Ceramics.

Microwave dielectric ceramics exhibiting a low dielectric constant (εr), high quality factor (Q × f), and thermal stability, specifically in an ultrawide temperature range (from -40 to +120 °C), have attracted much attention. In addition, the development of 5G communication has caused an urgent demand for electronic devices, such as dielectric resonant antennas. Hence, the feasibility of optimizing the dielectric properties of the SmNbO4 (SN) ceramics by substituting Bi3+ ions at the A site was studied. The permittivity principally hinges on the contribution of Sm/Bi-O to phonon absorption in the microwave range, while the reduced sintering temperature results in a smaller grain size and slightly lower Q × f value. The expanded and distorted crystal cell indicates that Bi3+ doping effectively regulates the temperature coefficient of resonant frequency (TCF) by adjusting the strains (causing the distorted monoclinic structure) of monoclinic fergusonite besides correlating with the permittivity. Moreover, a larger A-site radius facilitates the acquisition of near-zero TCF values. Notably, the (Sm0.875Bi0.125)NbO4 (SB0.125N) ceramic with εr ≈ 21.9, Q × f ≈ 38 300 GHz (at ∼8.0 GHz), and two different near-zero TCF values of -9.0 (from -40 to +60 °C) and -6.6 ppm/°C (from +60 to +120 °C), respectively, were obtained in the microwave band. A simultaneous increase in the phase transition temperature (Tc) and coefficients of thermal expansion (CTEs) by A-site substitution provides the possibility for promising thermal barrier coating (TBC) materials. Then, a cylindrical dielectric resonator antenna (CDRA) with a resonance at 4.86 GHz and bandwidth of 870 MHz was fabricated by the SB0.125N specimen. The exceptional performance shows that the SB0.125N material is a possible candidate for the sub-6 GHz antenna owing to the advantages of low loss and stable temperature.

Self-Nanocavity-Confined Halogen Anions Boosting the High Selectivity of the Two-Electron Oxygen Reduction Pathway over Ni-Based MOFs.

We present a strategy of self-nanocavity confinement for substantially boosting the superior electrochemical hydrogen peroxide (H2O2) selectivity for conductive metal-organic framework (MOF) materials. By using operando synchrotron radiation X-ray adsorption fine structure and Fourier transform infrared spectroscopy analyses, the dissociation of key *OOH intermediates during the oxygen reduction reaction (ORR) is effectively suppressed over the self-nanocavity-confined X-Ni MOF (X = F, Cl, Br, or I) catalysts, contributing to a favorable two-electron ORR pathway for highly efficient H2O2 production. As a result, the as-prepared Br-confined Ni MOF catalyst significantly promotes H2O2 selectivity up to 90% in an alkaline solution, evidently outperforming the pristine Ni MOF catalyst (40%). Moreover, a maximal faradic efficiency of 86% with a high cumulative H2O2 yield rate of 596 mmol gcatalyst-1 h-1 for electrochemical H2O2 generation is achieved by the Br-confined Ni MOF catalyst.

High-Pressure Structural Evolution of Disordered Polymeric CS2.

Carbon disulfide is an archetypal double-bonded molecule belonging to the class of group IV-group VI, AB2 compounds. It is widely believed that, upon compression to several GPa at room temperature and above, a polymeric chain of type (-(C═S)-S-)n, named Bridgman's black polymer, will form. By combining optical spectroscopy and synchrotron X-ray diffraction data with ab initio simulations, we demonstrate that the structure of this polymer is different. Solid molecular CS2 polymerizes at ∼10-11 GPa. The polymer is disordered and consists of a mixture of 3-fold (C3) and 4-fold (C4) coordinated carbon atoms with some C═C double bonds. The C4/C3 ratio continuously increases upon further compression to 40 GPa. Upon decompression, structural changes are partially reverted, while the sample also undergoes partial disproportionation. Our work uncovers the nontrivial high-pressure structural evolution in one of the simplest molecular systems exhibiting molecular as well as polymeric phases.

Structure, luminescence of Eu2+ and Eu3+ in CaMgSi2O6 and their co-existence for the excitation-wavelength/temperature driven colour evolution.

Luminescent materials with controllable colour evolution features are demanded for the development of multi-level anti-counterfeiting technologies. Here we report the structural and luminescence properties of CaMgSi2O6:Ln (Ln = Eu2+, Eu3+, Eu2+/3+) samples in detail and reveal their excitation-wavelength/temperature driven colour evolution characteristics. By tuning either the excitation-wavelength (276, 304, 343, 394 nm) or temperature (in the 330-505 K range), the designed samples with co-existing Eu2+/Eu3+ ions can achieve diverse and controllable colour evolution from red, to pink, purple and blue. This shows their potential application in anti-counterfeiting with the help of sophisticated pattern design. In addition, the underlying mechanism of the Stokes shift of the Eu2+ emission and valence stability of both Eu2+/Eu3+ ions in CaMgSi2O6 are also studied in depth. These results are valuable for designing colour-controllable luminescent materials based on the co-existence of the Eu2+/Eu3+ ions for anti-counterfeiting applications.

Structure and Microwave Dielectric Properties of Gillespite-Type ACuSi4O10 (A = Ca, Sr, Ba) Ceramics and Quantitative Prediction of the Q × f Value via Machine Learning.

Structure and dielectric properties of gillespite-type ceramics ACuSi4O10 (A = Ca, Sr, Ba) were investigated by crystal structure refinement, far-infrared reflectivity spectroscopy, and microwave dielectric measurements. A series of (CaxSr1-x)CuSi4O10 (0 < x < 1) ceramics with relative permittivities of 5.70-5.82, Q × f values of 20391-48794 GHz (@ ∼ 13.5 GHz), and τf of -46.3 to -38.9 ppm/°C were synthesized. By Ca2+ substitution for Sr2+ at the A-site, the rigid double-layered copper silicate framework remains stable, resulting in the nearly unchanged relative permittivity, while the [(Ca,Sr)O8] dodecahedron undergoes shrinkage and distortion, which is correlated to the changes in the Q × f and τf values. The normalized bond valence sums indicate that almost all ions are rattling, weakening the bond strengths and enlarging the molecular dielectric polarizability. The fitting of far-infrared reflectivity spectra reveals that the local structure changes suppress the intermediate and low-frequency vibrational modes significantly and improves the contribution from electronic polarization to permittivity. Symmetry breaking of the [(Ca,Sr)O8] dodecahedron conforms to the elevated restoring forces acting on the ions and improves the τf value. The large span in Q × f value may have intricate correlations to local structure changes and defects. Machine learning methods were introduced to explore the decisive structural factors for the Q × f value. A Q × f value prediction model correlated with the A-O2 bond length and the variance of A-O bond lengths was established. The Q × f values of isostructural (BaySr1-y)CuSi4O10 ceramics were predicted and verified by experiments.

Efficient Photoelectrochemical Conversion of Methane into Ethylene Glycol by WO3 Nanobar Arrays.

Photoelectrochemical (PEC) conversion of methane (CH4 ) has been extensively explored for the production of value-added chemicals, yet remains a great challenge in high selectivity toward C2+ products. Herein, we report the optimization of the reactivity of hydroxyl radicals (. OH) on WO3 via facet tuning to achieve efficient ethylene glycol production from PEC CH4 conversion. A combination of materials simulation and radicals trapping test provides insight into the reactivity of . OH on different facets of WO3 , showing the highest reactivity of surface-bound . OH on {010} facets. As such, the WO3 with the highest {010} facet ratio exhibits a superior PEC CH4 conversion efficiency, reaching an ethylene glycol production rate of 0.47 µmol cm-2 h-1 . Based on in situ characterization, the methanol, which could be attacked by reactive . OH to form hydroxymethyl radicals, is confirmed to be the main intermediate for the production of ethylene glycol. Our finding is expected to provide new insight for the design of active and selective catalysts toward PEC CH4 conversion.