Pyrazine-Functionalized Donor–Acceptor Covalent Organic Frameworks for Enhanced Photocatalytic H2 Evolution with High Proton Transport

The well-defined 2D or 3D structure of covalent organic frameworks (COFs) makes it have great potential in photoelectric conversion and ions conduction fields. Herein, a new donor–accepter (D–A) COF material, named PyPz-COF, constructed from electron donor 4,4′,4″,4′″-(pyrene-1,3,6,8-tetrayl)tetraaniline and electron accepter 4,4′-(pyrazine-2,5-diyl)dibenzaldehyde with an ordered and stable π-conjugated structure is reported. Interestingly, the introduction of pyrazine ring endows the PyPz-COF a distinct optical, electrochemical, charge-transfer properties, and also brings plentiful CN groups that enrich the proton by hydrogen bonds to enhance the photocatalysis performance. Thus, PyPz-COF exhibits a significantly improved photocatalytic hydrogen generation performance up to 7542 µmol g⁻¹ h⁻¹ with Pt as cocatalyst, also in clear contrast to that of PyTp-COF without pyrazine introduction (1714 µmol g⁻¹ h⁻¹). Moreover, the abundant nitrogen sites of the pyrazine ring and the well-defined 1D nanochannels enable the as-prepared COFs to immobilize H₃PO₄ proton carriers in COFs through hydrogen bond confinement. The resulting material has an impressive proton conduction up to 8.10 × 10⁻² S cm⁻¹ at 353 K, 98% RH. This work will inspire the design and synthesis of COF-based materials with both efficient photocatalysis and proton conduction performance in the future.     

Water-Stable Fluorous Metal–Organic Frameworks with Open Metal Sites and Amine Groups for Efficient Urea Electrocatalytic Oxidation

Urea oxidation reaction (UOR) is one of the promising alternative anodic reactions to water oxidation that has attracted extensive attention in green hydrogen production. The application of specifically designed electrocatalysts capable of declining energy consumption and environmental consequences is one of the major challenges in this field. Therefore, the goal is to achieve a resistant, low-cost, and environmentally friendly electrocatalyst. Herein, a water-stable fluorinated Cu(II) metalorganic framework (MOF) {[Cu₂(L)(H₂O)₂]·(5DMF)(4H₂O)}_n (Cu-FMOF-NH₂; H₄L = 3,5-bis(2,4-dicarboxylic acid)-4-(trifluoromethyl)aniline) is developed utilizing an angular tetracarboxylic acid ligand that incorporates both trifluoromethyl (–CF₃) and amine (–NH₂) groups. The tailored structure of Cu-FMOF-NH₂ where linkers are connected by fluoride bridges and surrounded by dicopper nodes reveals a 4,24T1 topology. When employed as electrocatalyst, Cu-FMOF-NH₂ requires only 1.31 V versus reversible hydrogen electrode (RHE) to deliver 10 mA cm⁻² current density in 1.0 m KOH with 0.33 m urea electrolyte and delivered an even higher current density (50 mA cm⁻²) at 1.47 V versus RHE. This performance is superior to several reported catalysts including commercial RuO₂ catalyst with overpotential of 1.52 V versus RHE. This investigation opens new opportunities to develop and utilize pristine MOFs as a potential electrocatalyst for various catalytic reactions.     

Discriminatory Gate-Opening Effect in a Flexible Metal–Organic Framework for Inverse CO2/C2H2 Separation

Considering the significant application of acetylene (C₂H₂) in the manufacturing and petrochemical industries, the selective capture of impurity carbon dioxide (CO₂) is a crucial task and an enduring challenge. Here, a flexible metal–organic framework (Zn-DPNA) accompanied by a conformation change of the Me₂NH₂⁺ ions in the framework is reported. The solvate-free framework provides a stepped adsorption isotherm and large hysteresis for C₂H₂, but type-I adsorption for CO₂. Owing to their uptakes difference before gate-opening pressure, Zn-DPNA demonstrated favorable inverse CO₂/C₂H₂ separation. According to molecular simulation, the higher adsorption enthalpy of CO₂ (43.1 kJ mol⁻¹) is due to strong electrostatic interactions with Me₂NH₂⁺ ions, which lock the hydrogen-bond network and narrow pores. Furthermore, the density contours and electrostatic potential verifies the middle of the cage in the large pore favors C₂H₂ and repels CO₂, leading to the expansion of the narrow pore and further diffusion of C₂H₂. These results provide a new strategy that optimizes the desired dynamic behavior for one-step purification of C₂H₂.     

A Metal–Organic Frameworks Derived 1T-MoS2 with Expanded Layer Spacing for Enhanced Electrocatalytic Hydrogen Evolution

Metal phase molybdenum disulfide (1T-MoS₂) is considered a promising electrocatalyst for hydrogen evolution reaction (HER) due to its activated basal and superior electrical conductivity. Here, a one-step solvothermal route is developed to prepare 1T-MoS₂ with expanded layer spacing through the derivatization of a Mo-based organic framework (Mo-MOFs). Benefiting from N,N-dimethylformamide oxide as external stress, the interplanar spacing of (002) of the MoS₂ catalyst is extended to 10.87 Å, which represents the largest one for the 1T-MoS₂ catalyst prepared by the bottom-up approach. Theoretical calculations reveal that the expanded crystal planes alter the electronic structure of 1T-MoS₂, lower the adsorption–desorption potentials of protons, and thus, trigger efficient catalytic activity for HER. The optimal 1T-MoS₂ catalyst exhibits an overpotential of 98 mV at 10 mA cm⁻² for HER, corresponding to a Tafel slope of 52 mV dec⁻¹. This Mo-MOFs-derived strategy provides a potential way to design high-performance catalysts by adjusting the layer spacing of 2D materials.     

MOF-Derived Mn2O3 Nanocage with Oxygen Vacancies as Efficient Cathode Catalysts for Li–O2 Batteries

Designing efficient and cost-effective electrocatalysts is the primary imperative for addressing the pivotal concerns confronting lithium–oxygen batteries (LOBs). The microstructure of the catalyst is one of the key factors that influence the catalytic performance. This study proceeds to the advantage of metal-organic frameworks (MOFs) derivatives by annealing manganese 1,2,3-triazolate (MET-2) at different temperatures to optimize Mn₂O₃ crystals for special microstructures. It is found that at 350 °C annealing temperature, the derived Mn₂O₃ nanocage maintains the structure of MOF, the inherited high porosity and large specific surface area provide more channels for Li⁺ and O₂ diffusion, beside the oxygen vacancies on the surface of Mn₂O₃ nanocages enhance the electrocatalytic activity. With the synergy of unique structure and rich oxygen vacancies, the Mn₂O₃ nanocage exhibits ultrahigh discharge capacity (21 070.6 mAh g⁻¹ at 500 mA g⁻¹) and excellent cycling stability (180 cycles at the limited capacity of 600 mAh g⁻¹ with a current of 500 mA g⁻¹). This study demonstrates that the Mn₂O₃ nanocage structure containing oxygen vacancies can significantly enhance catalytic performance for LOBs, which provide a simple method for structurally designed transition metal oxide electrocatalysts.     

Plasmonic Metal Mediated Charge Transfer in Stacked Core–Shell Semiconductor Heterojunction for Significantly Enhanced CO2 Photoreduction

Construction of core–shell semiconductor heterojunctions and plasmonic metal/semiconductor heterostructures represents two promising routes to improved light harvesting and promoted charge separation, but their photocatalytic activities are respectively limited by sluggish consumption of charge carriers confined in the cores, and contradictory migration directions of plasmon-induced hot electrons and semiconductor-generated electrons. Herein, a semiconductor/metal/semiconductor stacked core–shell design is demonstrated to overcome these limitations and significantly boost the photoactivity in CO₂ reduction. In this smart design, sandwiched Au serves as a “stone”, which “kills two birds” by inducing localized surface plasmon resonance for hot electron generation and mediating unidirectional transmission of conduction band electrons and hot electrons from TiO₂ core to MoS₂ shell. Meanwhile, upward band bending of TiO₂ drives core-to-shell migration of holes through TiO₂–MoS₂ interface. The co-existence of TiO₂ → Au → MoS₂ electron flow and TiO₂ → MoS₂ hole flow contributes to spatial charge separation on different locations of MoS₂ outer layer for overall redox reactions. Additionally, reduction potential of photoelectrons participating in the CO₂ reduction is elaborately adjusted by tuning the thickness of MoS₂ shell, and thus the product selectivity is delicately regulated. This work provides fresh hints for rationally controlling the charge transfer pathways toward high-efficiency CO₂ photoreduction.     

Formation of C?X Bonds in CO2 Chemical Fixation Catalyzed by Metal−Organic Frameworks

Transformation of CO₂ based on metal−organic framework (MOF) catalysts is becoming a hot research topic, not only because it will help to reduce greenhouse gas emission, but also because it will allow for the production of valuable chemicals. In addition, a large number of impressive products have been synthesized by utilizing CO₂. In fact, it is the formation of new covalent bonds between CO₂ and substrate molecules that successfully result in CO₂ solidly inserting into the products, and only four types of new C X bonds, including C H, C C, C N, and C O bonds, are observed in this exploration. An overview of recent progress in constructing C X bonds for CO₂ conversion catalyzed by various MOF catalysts is provided. The catalytic mechanism of generating different C X bonds is further discussed according to both structural features of MOFs and the interactions among CO₂, substrates, as well as MOFs. The future opportunities and challenges in this field are also tentatively covered.     

Oxidation of Fe–Si alloys in CO2–H2O atmospheres

Abstract

Iron and model alloys containing 1, 2, and 3wt% Si were reacted with dry and wet CO₂ gases at 800°C. All oxidised in dry CO₂ according to approximately linear kinetics. Additions of H₂O accelerated the reaction until steady-state parabolic kinetics were achieved. However, the effect of H₂O was small in the steady-state reaction stage of Fe – 3Si. Alloy reaction products were a duplex scale consisting of an outer FeO+Fe₃O₄ layer and an inner FeO+Fe₂SiO₄ layer, plus an internal oxidation zone, in all gases. In Fe – 1Si, amorphous SiO₂ precipitates in the internal oxidation zone grew with rod-like morphologies in all gases. However, internal amorphous SiO₂ precipitates grown in Fe – 2Si and Fe – 3Si formed network patterns. Internal penetration rates were initially rapid in Fe – 1Si, but slowed considerably at longer times. In Fe – 3Si, the internal oxidation zone grew wider in the first 20 h of reaction, and then remained constant in dry gas. In the wet gases this zone subsequently diminished, and disappeared after 50 h reaction.     

Single-Site Metal–Organic Framework and Copper Foil Tandem Catalyst for Highly Selective CO2 Electroreduction to C2H4

Tandem catalysis is a promising way to break the limitation of linear scaling relationship for enhancing efficiency, and the desired tandem catalysts for electrochemical CO₂ reduction reaction (CO₂RR) are urgent to be developed. Here, a tandem electrocatalyst created by combining Cu foil (CF) with a single-site Cu(II) metal–organic framework (MOF), named as Cu–MOF–CF, to realize improved electrochemical CO₂RR performance, is reported. The Cu–MOF–CF shows suppression of CH₄, great increase in C₂H₄ selectivity (48.6%), and partial current density of C₂H₄ at −1.11 V versus reversible hydrogen electrode. The outstanding performance of Cu–MOF–CF for CO₂RR results from the improved microenvironment of the Cu active sites that inhibits CH₄ production, more CO intermediate produced by single-site Cu–MOF in situ for CF, and the enlarged active surface area by porous Cu–MOF. This work provides a strategy to combine MOFs with copper-based electrocatalysts to establish high-efficiency electrocatalytic CO₂RR.     

Oxidation of FeCrAl foils at 500–900°C in dry O2 and O2 with 40% H2O

Abstract

High temperature resistant FeCrAl alloys are frequently used in high temperature applications such as heating elements and metal based catalytic converter bodies. When exposed to high temperatures an adherent, slowly growing, dense aluminium oxide layer forms on the surface, which protects the underlying alloy from severe degradation. The composition, structure and properties of the formed oxide layer are strongly dependent on the alloy composition, temperature and oxidation environment. In this study, the Sandvik 0C404 FeCrAl alloy, in the form of 50 μm thick foils, was exposed isothermally in the temperature range 500–900°C for 168 hours in dry O₂ and in O₂ with 40 vol.% H₂O. The surface morphology, composition and microstructure of the grown oxide scales were characterized by using scanning electron microscopy (SEM), transmission electron microscopy (TEM), energy dispersive X-ray spectroscopy (EDX), grazing incidence X-ray diffraction (GIXRD), Auger electron spectroscopy (AES), and time of flight secondary ion mass spectrometry (TOF-SIMS). The oxidation process was faster at 900°C than at 500 and 700°C. At 500°C a thin (10–20 nm) mixed oxide of Fe, Cr and Al was formed. Exposure at 700°C resulted in a similar (40–50 nm) duplex oxide, in both dry O₂ and in O₂ with 40 vol.% H₂O. These oxide scales consisted of an inner and an outer relatively pure alumina separated by a Cr-rich band. This type of duplex oxide scale also formed at 900°C with a thin inward growing α–Al₂O₃ at the oxide/metal interface and an outward growing layer outside a Cr-rich band. However, at 900°C the outward growing layer showed two types of oxide morphologies; a thin smooth base oxide and a much thicker nodular oxide grown on top of substrate ridges. In dry O₂ atmosphere, the main part of this outward growing layer had transformed to α–Al₂O₃. Only in the outer part of the thick oxide nodules, metastable alumina was found. When exposed in the presence of water vapour the main part of the metastable alumina remained untransformed.     

Vortex Lattice Melting in YBa2Cu4O8 with H∥ab

We report c-axis resistivity measurements in the mixed state of YBa₂Cu₄O₈ with the magnetic field applied parallel to the a-, b-, and c-axes. For all orientations of the magnetic field, a kink is observed in the resistive transition, associated with the first-order melting of an anisotropic three-dimensional vortex lattice. Whereas the melting lines for Hb and Hc obey the expected relation H _m = H ₀(1 – T/T _c ) ⁿ with n = 1.5, H _m (T) for Ha follows a different temperature dependence with a lower exponent. This result is consistent with a suppression of the melting line due to a reduction in the dimensionality of YBa₂Cu₄O₈ in this field geometry, as observed in normal-state magnetoresistance measurements.     

Metal-free π-conjugated hybrid g-C3N4 with tunable band structure for enhanced visible-light photocatalytic H2 production

Development of low-cost and efficient photocatalytic materials with visible-light response is of urgent need for solving energy and environmental problems.Here,a metal-free two-dimensional (2D) π-conjugated hybrid g-C3N4 photocatalyst with tunable band structure was prepared by a novel one-pot bottom-up method based on a supersaturated precipitation process of urea and triethanolamine (TEOA)solution.The microstructure of the hybrid g-C3N4 is revealed to be a compound of periodic tri-s-triazine units grafted with N-doped graphene (GR) fragments.From experimental evidence and theoretical calcu-lations,the two different π-conjugated fragments in the hybrid g-C3N4 material are proved to construct a 2D in-plane junction structure,thereby expanding the light absorption range and accelerating the inter-face charge transfer.The π-conjugated electron coupling in the 2D photocatalyst eliminates the grain boundary effect,and the coupled highest occupied molecular orbital (HOMO) effectively promotes the separation of photo-induced charge carriers.Compared with the g-C3N4 prepared by the conventional method,the visible-light H2 production activity of the optimized sample is enhanced by 253 ％.This work provides a new strategy of constructing metal-free g-C3N4 hybrids for efficient photocatalytic water splitting.     

Turn “Waste” Into Wealth: MoO2@coal Gangue Electrocatalyst with Amorphous/Crystalline Heterostructure for Efficient Li–O2 Batteries

Unreasonable accumulation of coal gangue in mining area has become the major source of global pollution. Probing the high-valued utilization of coal gangue has become a key approach to address the problem. Herein, a promising catalyst of MoO₂@coal gangue with amorphous/crystalline heterostructure derived from mine solid waste, which acts as an efficient cathode for Li–O₂ batteries is first reported. Impressively, the as-prepared catalyst exhibits a favorable initial discharge capacity of 9748 mAh g⁻¹ and promising long-term cyclic stability over 2200 h. Experimental results coupled with density functional theory (DFT) analysis reveal that the synergistic interaction between high-activity MoO₂ and stable SiO₂, unique amorphous/crystalline heterostructure and the modified interfacial adsorption of LiO₂ intermediate are critical factors in promoting the electrochemical performance. This work provides a new insight to design marked electrocatalysts by mine solid waste for Li–O₂ batteries.     

Dielectric resonators with complex crystal structures in the La2O3–Al2O3–TiO2 system for microwave applications

LaTi₂Al₉O₁₉ and La₃Ti₅Al₁₅O₃₇ ceramics in the La₂O₃–Al₂O₃–TiO₂ system have been prepared by conventional solid state ceramic route. The structure and microstructure of the compositions have been studied using powder X-ray diffraction and scanning electron microscopic techniques. Laser Raman studies have been employed to understand the complex crystal structure of these compositions in molecular level. The microwave dielectric properties of the sintered ceramic compacts were measured by Hakki and Colemann post resonator and TE_01δ cavity techniques using a vector network analyzer. LaTi₂Al₉O₁₉ and La₃Ti₅Al₁₅O₃₇ ceramics possess excellent microwave dielectric properties such as relatively high unloaded quality factors 7,762 and 7,415, low dielectric constant 15.7 and 22.1 and low temperature coefficient of resonant frequency values ?22 and +18.9 ppm/°C, respectively.     

Correcting for methane interferences on δ2H and δ18O measurements in pore water using H2Oliquid-H2Ovapor equilibration laser spectroscopy

Cavity ring-down spectroscopy (CRDS) is a new and evolving technology that shows great promise for isotopic δ(18)O and δ(2)H analyses of pore water from equilibrated headspace H(2)O vapor from environmental and geologic cores. We show that naturally occurring levels of CH(4) can seriously interfere with CRDS spectra, leading to erroneous δ(18)O and δ(2)H results for water. We created a new CRDS correction algorithm to account for CH(4) concentrations typically observed in subsurface and anaerobic environments, such as ground waters or lake bottom sediments. We subsequently applied the correction method to a series of geologic cores that contain CH(4). The correction overcomes the spectral interference and provides accurate pore water δ(18)O and δ(2)H values with acceptable precision levels as well as accurate concentrations of CH(4).     

Porous Host–Guest MOF-Semiconductor Hybrid with Multisites Heterojunctions and Modulable Electronic Band for Selective Photocatalytic CO2 Conversion and H2 Evolution

Optimizing catalysts for competitive photocatalytic reactions demand individually tailored band structure as well as intertwined interactions of light absorption, reaction activity, mass, and charge transport.  Here, a nanoparticulate host–guest structure is rationally designed that can exclusively fulfil and ideally control the aforestated uncompromising requisites for catalytic reactions. The all-inclusive model catalyst consists of porous Co₃O₄ host and Zn_xCd_1-xS guest with controllable physicochemical properties enabled by self-assembled hybrid structure and continuously amenable band gap. The effective porous topology nanoassembly, both at the exterior and the interior pores of a porous metal–organic framework (MOF), maximizes spatially immobilized semiconductor nanoparticles toward high utilization of particulate heterojunctions for vital charge and reactant transfer. In conjunction, the zinc constituent band engineering is found to regulate the light/molecules absorption, band structure, and specific reaction intermediates energy to attain high photocatalytic CO₂ reduction selectivity. The optimal catalyst exhibits a H₂-generation rate up to 6720 µmol g⁻¹ h⁻¹ and a CO production rate of 19.3 µmol g⁻¹ h⁻¹. These findings provide insight into the design of discrete host–guest MOF-semiconductor hybrid system with readily modulated band structures and well-constructed heterojunctions for selective solar-to-chemical conversion.     

TEM investigation of the oxide scales formed on a FeCrAlRE alloy (Kanthal AF) at 900°C in dry O2 and O2 with 40% H2O

Abstract

The base oxide scales on a commercial FeCrAl alloy oxidized isothermally at 900°C in dry O₂ or O₂ with 40% H₂O were studied in detail using analytical electron microscopy. Electron transparent cross-section foils prepared with a FIB/SEM in-situ lift-out technique were investigated using STEM/EDX and CBED. The oxide scales on the samples exposed to dry O₂ are slightly thinner than the scales formed in O₂+H₂O. The oxide scales exhibit a multilayered structure, with a Cr-rich layer in the middle, indicating the original metal/gas interface. An almost pure inner α-Al₂O₃ layer, containing columnar grains, was formed by inward oxygen diffusion, after exposures in both the dry and wet atmospheres. The outer oxide layer consisted of γ-Al₂O₃ in the wet case and of α-Al₂O₃/MgAl₂O₄ in the dry case. It is suggested that the α-Al₂O₃/MgAl₂O₄ phases resulted from a phase transformation of initially grown γ-Al₂O₃. The observations indicate that water vapour may stabilize the γ-Al₂O₃ phase.     

Preparation and Properties of Li2Zn3Ti4O12-Based Ceramics with a Sintering Aid in the Li2O–B2O3–SiO2 System for LTCC Technology

Inorganic Materials - Using powders synthesized under optimal conditions, we have prepared Li2Zn3Ti4O12 + ZnTiO3 ceramics suitable for designing microelectronic components by low-temperature...     

Phase Relations in the Na2CO3–ZrO2–SiO2–H2O System at 0.1 and 0.05 GPa and 450°C

The phase relations in the Na₂CO₃–ZrO₂–SiO₂–H₂O system were studied at 0.1 and 0.05 GPa and 450°C using large-particle-size and nanocrystalline zirconias. Four silicates were obtained when use was made of readily soluble ZrO₂(nanocr): ZrSiO₄, Na₂ZrSi₆O₁₅ · 3H₂O, Na₂ZrSi₃O₉ · 2H₂O, and Na₄Zr₂Si₅O₁₆ · H₂O. In the system containing poorly soluble ZrO₂(cr), only Na₂ZrSi₆O₁₅ · 3H₂O was found to crystallize. It is shown that the structures of all the Na–Zr silicates contain invariant six-polyhedron structural precursors, each made up of two ZrO₆ octahedra and four SiO₄ tetrahedra, and belong to a homologous series of structures based on the silicate Na₂ZrSi₂O₇, which forms via direct packing of cyclic subpolyhedral precursors.     

N-doped reduced graphene oxide anchored with δTa2O5 for energy and environmental remediation: Efficient light-driven hydrogen evolution and simultaneous degradation of textile dyes

Precipitation assisted facile hydrothermal method has been developed for anchoring nitrogen-doped reduced graphene oxide (NRGO) with tantalum pentoxide (TO) denoted as TO@NRGO. Synthesized materials were characterized using spectroscopic, optical and microscopic techniques and confirm transforming TO from orthorhombic to hexagonal phase (δ) upon anchoring with NRGO. TO@NRGO, TO and NRGO have been evaluated for photocatalytic hydrogen evolution, degradation of Methylene blue (MB) and Rhodamine B (RhB). The enhanced photocatalytic activity was observed in TO@NRGO nanocomposite compared to TO and NRGO due to decreased bandgap (2.5 eV) and increased surface area (312 m² g^?1). TO@NRGO evolved 19,500 µmol g^?1 of hydrogen for 3 h. TO@NRGO showed better degradation efficiency of 94 and 88% at a time of 100 min for MB and RhB, respectively. The parameters involved in photocatalytic dye degradation, like the effect of pH, catalyst dosage, and initial concentration of dyes, have been carefully optimized to achieve maximum performance of the catalyst. The stability and reusability of TO@NRGO are good and managed to degrade dyes effectively even after the 5th run. Thus, TO@NRGO could serve as a choice of material in resolving the issues related to energy and the environment.