Alkali Metal Research Articles

Structural Distortions and Short‐Range Magnetism in a Honeycomb Iridate Cu3ZnIr2O6

Layered honeycomb iridates receive significant attention in the materials chemistry and physics fields due to the relevance of their crystal structures to the Kitaev model of a quantum spin liquid (QSL). In quest of liquid‐like magnetic ground state signatures, first‐generation alkali metal iridates A2IrO3 ≡ A3[AIr2]O6 (A = Li, Na) and second‐generation iridates T3[AIr2]O6 (T = Cu, Ag, H) are developed. T3[AIr2]O6 is synthesized from A3[AIr2]O6 via metathesis reactions replacing alkali ions located between honeycomb layers. Herein, the next level of chemical and structural complexity is introduced by synthesizing the honeycomb iridate, Cu3ZnIr2O6, in which alkali ions between and within the honeycomb layers are both selectively exchanged with two different transition metals. Analysis of powder X‐Ray diffraction data reveals corrugation of the honeycomb layers in Cu3ZnIr2O6 that hinders complete magnetic frustration and results in a spin glass behavior observed from magnetization and specific heat data. Thus, Cu3ZnIr2O6 represents yet another model, which broadens understanding of intricate relationships between intralayer distortions and magnetism of prospective Kitaev QSL compounds.

Numerical method research and characteristics analysis on frozen start-up process of high-temperature heat pipe

Future space exploration technology requires a long-life and reliable power source that is not reliant on solar energy. Space micro-reactors are able to meet this need, with Heat Pipe Cooled Reactors (HPR) emerging as a notable type of space micro-reactor that has attracted widespread attention in recent years. The HPR utilizes high-temperature alkali metal heat pipes for heat transfer, which presents certain complexities due to the solid state of the alkali metals working medium at room temperature. This results in a three-phase transition during the high-temperature heat pipes start-up process, which significantly impacts the heat transfer characteristics and dynamic behavior of the HPR start-up process. Consequently, thorough research is necessary in this area. Numerical simulation is a crucial tool that can effectively analyze, predict, and guide experiments. This article utilizes the Finite Volume Method (FVM) to develop a simulation code for high-temperature heat pipe frozen start-up. Various physical models are integrated to describe different components of the heat pipe: the container is represented by a two-dimensional axisymmetric heat conduction equation, the wick region utilizes a Fixed Grid Method (FGM) to depict the melting process of the medium, and the vapor channel is described through a two-dimensional axisymmetric compressible laminar flow. The wick region and vapor channel are coupled through the evaporation and condensation of the medium. For the vapor channel, numerical methods such as SIMPLE and PISO are used for solving. Adaptive time step and OpenMP acceleration are employed in the code to enhance computational efficiency. Finally, by comparing the calculated results with experimental data, the feasibility and accuracy of the code are assessed, highlighting special phenomena during the start-up process. The findings confirm that the developed code accurately predicts parameter changes during start-up, and can serve as a heat pipe analysis module for multi-physics coupling analysis of HPR.

Thermally stimulated color-tunable performance of Ca3Ga4O9: Bi3+ by co-doping with alkali metal ions

Thermally stimulated color-tunable persistent luminescent materials can serve in many practical applications. Integrating color-tunable luminescence into a stable charge carrier trapping phosphor is a promising strategy but remains a challenge. In this work, by co-doping with alkali metal ions, Ca2.90Ga4O9: 5 mol% Bi3+, 5 mol% A+ (A+= Li+, Na+, K+) phosphors show noticeable thermal stimulated luminescence color-tunability. Among these samples, the phosphor co-doped with Na+ shows a dramatic color variation with temperature from cyan (513 nm) at 99 °C to yellow (602 nm) at 237 ℃. Further studies confirm that the thermally stimulated color-tunable feature of the sample is attributed to the interplay between dual traps and different emission centers. This work reports the dynamic color-tunable persistent luminescence under different temperatures in alkali metal ions co-doped gallate and provides a new perspective for the design of thermally responsive dynamic optical materials for the application of visual temperature warning or counterfeiting.

Nuclear-excited source of coherent and incoherent radiation with direct nuclear pumping

Uranium fission fragments, as well as the products of 3He(n,p)3H and 10B(n,α)7Li nuclear reactions were utilized in the nuclear reactor for gas ionization and excitation. However, the 6Li(n,α)3H nuclear reaction was less examined. The use of lithium-6 as a surface source of excitation of the gas medium, due to the long path length of tritium nuclei in the gas, allows to excite large volumes of gas as opposed to using 235U or 10B.While investigating the luminescence of noble gases in the core of the IVG.1M research reactor, we noted an appearance of alkali metal lines and a sharp increase in the intensity of these lines at temperatures above 570 K. It was determined that the population of levels of lithium atoms has practically no effect on the population of the 2p-levels of atoms of noble gases. The selectivity of p- and s-levels deactivation by lithium atoms implies the possibility of creating inversion of population at 2p-1s transitions of noble gas atoms. Successful experiments to study the luminescence of gases upon excitation by 6Li(n,α)3H nuclear reaction products allow us to proceed to experiments to achieve the laser action threshold and study the lasing characteristics of gas mixtures at the IGR pulsed nuclear reactor with thermal neutron flux density up to 7∙1016 n/cm2s. For this purpose, an experimental device designs were proposed to perform experiments on the IGR reactor. A step-by-step procedure of fabrication of a nuclear-excited source for excitation of gas mixtures is provided. The results of reactor experiments aimed at determining the spectral and temporal characteristics of optical radiation during excitation of gas mixtures by 6Li(n,α)3H nuclear reaction products are presented.

Effect of ion-specific water structures at metal surfaces on hydrogen production

Water structures at electrolyte/electrode interfaces play a crucial role in determining the selectivity and kinetics of electrochemical reactions. Despite extensive experimental and theoretical efforts, atomic-level details of ion-specific water structures on metal surfaces remain unclear. Here we show, using scanning tunneling microscopy and noncontact atomic force microscopy, that we can visualize water layers containing alkali metal cations on a charged Au(111) surface with atomic resolution. Our results reveal that Li+ cations are elevated from the surface, facilitating the formation of an ice-like water layer between the Li+ cations and the surface. In contrast, K+ and Cs+ cations are in direct contact with the surface. We observe that the water network structure transitions from a hexagonal arrangement with Li+ to a distorted hydrogen-bonding configuration with Cs+. These observations are consistent with surface-enhanced infrared absorption spectroscopy data and suggest that alkali metal cations significantly impact hydrogen evolution reaction kinetics and efficiency. Our findings provide insights into ion-specific water structures on metal surfaces and underscore the critical role of spectator ions in electrochemical processes.

A pilot study on a 30 t/h biomass gasification-combustion plant

As a renewable energy with zero carbon emission, the utilization of biomass has attracted widely studied. One of the most effective methods is to gasify the biomass into high-quality gas fuel. In the recent years, the majority of research on biomass gasification is conducted in the laboratory. However, it lacks the research in engineering application scale. In this work, a biomass gasification-combustion plant was designed and built to provide the industrial steam with a rate of 30 t/h for a food industrial park. The agricultural and forestry waste biomass was gasified in a gasifier, and then the product gas combusted in a boiler to supply the steam. The characteristics of the product gas from the gasifier were studied. The corrosion and pollutants in the combustion process were investigated. In the gasification process, the main components of the product gas are CO, H2 and CH4. CO and H2 account for 29.55 vol%-30.56 vol% and 11.65 vol%-15.35 vol%, respectively. The calorific value of the product gas is 5.88–6.29 MJ/m3. The tar concentration is 110.58–155.07 g/Nm3. At the outlet of the boiler, the concentration of the filterable particulate matter is 300.25 mg/Nm3, and the particle size is concentrated at 1.00–2.50 μm. The concentration of the condensable particulate matter (CPM) is 157.14 mg/Nm3, and the proportion of water-soluble ions in CPM is 86.36 wt%. The concentration of Cl−, SO42-, NH4+ and Na+ in CPM is relatively high, with the values of 28.83 mg/Nm3, 10.29 mg/Nm3, 7.46 mg/Nm3, and 5.06 mg/Nm3, respectively. During the half-year running, the ash deposition and corrosion were detected in the boiler heating surface and the economizer. The ash deposit in the boiler is mainly composed of the sulfate and silicate, such as CaSO4, Zn2SO4, Na2SO4 and K3Na(SO4)2. The ash deposit in the economizer is primarily composed of the sulfate and a small amount of alkali metal chloride. The flue gas reaches the emission requirement after passing through the pollution control devices and can be discharged into the atmosphere.

Effect of HTC and Water-Leaching of Low-Grade Biomasses on the Release Behavior of Inorganic Constituents in a Calcium Looping Gasification Process at 650 °C.

The release of alkali metals (K, Na) and nonmetals (S, Cl) during a calcium looping (CaL) gasification process of waste derived-hydrochars, water-leached samples, and CaO-biomass blends was investigated. Special attention was paid to biomasses that are not particularly promising for gasification requirements but have a large occurrence in Europe, including Grape Bagasse, Organic Fraction of Municipal Solid Waste (OFMSW), Green Waste, and Out-of-use woods from construction debris and discarded furniture. The release experiments were performed at 650 °C in a flow channel reactor to investigate the behavior of inorganic trace substances. Hot-gas analysis was performed by Molecular Beam Mass Spectrometry (MBMS). Thermodynamic equilibrium calculations via FactSage indicate H2S, carbonyl sulfide (COS), KCl, NaCl, and HCl as the main inorganic impurities. Thus, the focus of the experiments was placed on these species. It was found that the concentrations of trace elements released during gasification at 650 °C, such as H2S, SO2, KCl, and NaCl, are hardly affected by intense water-leaching. In contrast, carbonaceous materials from hydrothermal carbonization exhibit a higher concentration of trace potassium substances (K, KCl, and K2Cl+). When biomass samples are combined with CaO, the total amount of inorganic trace compounds (K, Na, and S compounds) in the resulting syngas could be decreased.

Conformation and Photodissociation Process of Benzo-15-Crown-5 and Benzo-18-Crown-6 Complexes with Ammonium Ions Investigated by Cold UV and IR Spectroscopy in the Gas Phase.

We examined the conformation of benzo-15-crown-5 (B15C5) and benzo-18-crown-6 (B18C6) complexes with ammonium ions, NH4+, CH3NH3+ (MeNH3+), CH3CH2NH3+ (EtNH3+), and CH3CH2CH2NH3+ (PrNH3+), using cold UV and IR spectroscopy in the gas phase. We measured the UV photodissociation (UVPD) spectra of the ammonium complexes and compared them with those of the K+(B15C5) and K+(B18C6) complexes in order to identify the conformation on the basis of the band position. The number of possible conformations for the ammonium complexes of B15C5 is limited compared with alkali metal ions with similar ionic radii. The NH4+(B15C5), MeNH3+(B15C5), and EtNH3+(B15C5) complexes show two conformers, whereas the K+(B15C5) complex has three stable conformers. In the case of the PrNH3+(B15C5) complex, one conformer was found predominantly in the UVPD spectrum. The ammonium complexes of B15C5 prefer to adopt crown conformations with large dihedral angles on the C-O-C-C atoms around the benzene moiety. In the case of the ammonium complexes of B18C6, two or three conformers were found in the UVPD spectra. One conformation of the B18C6 complexes is similar to that of the K+(B18C6) complex, which has a planar form on the C-O-C-C atoms around the benzene moiety. The other but dominant conformations of the ammonium complexes could be attributed to those with large C-O-C-C dihedral angles. These conformational findings for the ammonium complexes suggest that the benzo-crown ethers tend to adopt nonplanar conformations around the benzene moiety to encapsulate the ammonium ions. The IR-UV double-resonance (DR) spectra of the B15C5 and B18C6 complexes were compared to those of benzo-12-crown-4 (B12C4) and dibenzo-18-crown-6 (DB18C6) complexes. The N-H···O hydrogen bond (H-bond) is weaker with increasing ring size from B12C4 to B18C6, although the calculated binding energy is smaller for B12C4 than for B18C6. This result indicates that cooperative H-bonds with three N-H groups can strengthen the intermolecular bond between the ammonium ions and B18C6. The difference in the conformational preference between the ammonium and K+ complexes is attributed to directed N-H···O H-bonds in the ammonium complexes. Proton transfer and dissociation of the crown ring were also observed for the photoexcitation of the NH4+(B15C5) and NH4+(B18C6) complexes.

Designing electrolytes with high solubility of sulfides/disulfides for high-energy-density and low-cost K-Na/S batteries

Alkaline metal sulfur (AMS) batteries offer a promising solution for grid-level energy storage due to their low cost and long cycle life. However, the formation of solid compounds such as M2S2 and M2S (M = Na, K) during cycling limits their performance. Here we unveil intermediate-temperature K-Na/S batteries utilizing advanced electrolytes that dissolve all polysulfides and sulfides (K2Sx, x = 1–8), significantly enhancing reaction kinetics, specific capacity, and energy density. These batteries achieve near-theoretical capacity (1655 mAh g−1 sulfur) at 75 °C with a 1 M sulfur concentration. At a 4 M sulfur concentration, they deliver 830 mAh g−1 at 2 mA cm−2, retaining 71% capacity after 1000 cycles. This new K-Na/S battery with specific energy of 150-250 Wh kg−1 only employs earth-abundant elements, making it attractive for long-duration energy storage.

Secondary metal ion-induced electrochemical reduction of U(VI) to U(IV) solids

Recent studies have shown that aqueous U(VI) ions can be transformed into U(VI) precipitates through electrocatalytic redox reactions for uranium recovery. However, there have been no reports of U(IV) solids, such as UO2, using electrochemical methods under ambient conditions since low-valence states of uranium are typically oxidized to U(VI) by O2 or H2O2. Here we developed a secondary metal ion-induced strategy for electrocatalytic production of U(IV) solids from U(VI) solutions using a catalyst consisting of atomically dispersed gallium on hollow nitrogen-doped carbon capsules (Ga-Nx-C). This method relies on the presence of secondary metal ions, e.g., alkaline earth metals, transition metals, lanthanide metals, and actinide metals, which promote the generation of UO2 or bimetallic U(IV)-containing oxides through a two-electron transfer process. No U(IV) solid products were generated in the presence of alkali metal ions. Mechanistic studies revealed that the strong binding affinity between U(IV) and alkaline earth metals (Ca2+/Mg2+/Sr2+/Ba2+), transition metals (Ni2+/Zn2+/Pb2+/Fe3+, etc.) and lanthanide/actinide metals (Ce4+/Eu3+/Th4+/La3+) suppressed re-oxidation of U(IV) to U(VI), leading to the generation of U(IV)O2 and Mx(M = Ce, Eu, Th, La)U(IV)yO2. This work provides fundamental insights into the electrochemical behavior of uranium in aqueous media, whilst guiding uranyl capture from nuclear waste and contaminated water.

CaY@C2n: Exploring Molecular Qubits with Ca-Y Metal-Metal Bonds.

Metal-metal bonding is crucial in chemistry for advancing our understanding of the fundamental aspects of chemical bonds. Metal-metal bonds based on alkaline-earth (Ae) elements, especially the heavier Ae elements (Ca, Sr, and Ba), are rarely reported due to their high electropositivity. Herein, we report two heteronuclear di-EMFs CaY@Cs(6)-C82 and CaY@C2v(5)-C80, which contain unprecedented single-electron Ca-Y metal-metal bonds. These compounds were characterized by single-crystal X-ray crystallography, electron paramagnetic resonance (EPR) spectroscopy, and DFT calculations. The crystallographic study of CaY@Cs(6)-C82 shows that Ca and Y are successfully encapsulated into the carbon cage with a Ca-Y distance of 3.691 Å. The CW-EPR study of both CaY@Cs(6)-C82 and CaY@C2v(5)-C80 exhibits a doublet, suggesting the presence of an unpaired electron located between Ca and Y. The combined experimental and theoretical results confirm the presence of a Ca-Y single-electron metal-metal bond with substantial covalent interaction, attributed to significant overlap between the 4s4p orbitals of Ca and the 5s5p4d orbitals of Y. Furthermore, pulse EPR spectroscopy was used to investigate the quantum coherence of the electron spin within this bond. The unpaired electron, characterized by its s orbital nature, is effectively protected by the carbon cage, resulting in efficient suppression of both spin-lattice relaxation and decoherence. CaY@Cs(6)-C82 behaves as an electron spin qubit, displaying a maximum decoherence time of 7.74 μs at 40 K. This study reveals an unprecedented Ae-rare-earth metal-metal bond stabilized by the fullerene cages and elucidates the molecular qubit properties stemming from their unique bonding character, highlighting their potential in quantum information processing applications.

An Azide-Free Synthesis of Metallodiazomethanes Using Nitrous Oxide.

Diazo compounds are valuable reagents in synthesis but usually require the use of potentially explosive or toxic starting materials. Here, we report the synthesis and isolation of alkali metal diazomethanides by the reaction of metalated ylides with nitrous oxide, resulting in a formal exchange of the phosphine ligand by dinitrogen. The reaction proceeds through a Wittig-like mechanism via a [3 + 2] cycloaddition of N2O across the ylide bond with release of phosphine oxide. The metalated diazomethanes exhibit an increased thermal stability due to the stronger binding of N2 compared to neutral diazomethanes. This is reflected in short C-N distances and red-shifted N-N vibrations and enables versatile applications such as for the preparation of transition metal diazomethanide complexes and the synthesis of 1,2,3-triazoles from nitriles, diazoacetates from carbon dioxide, or alkynes from aldehydes.

Size-Dependent Isovalent Impurity Doping for Ambipolar Control in Cu3N.

Substitutional doping, involving the replacement of a host with an aliovalent impurity ion, is widely used to attain ambipolar controllability in semiconductors, which is crucial for device application. However, its effectiveness for p-type doping is limited in monovalent cation compounds due to the lack of suitable aliovalent (i.e., zerovalent) impurities. We propose an alternative approach for p- and n-type doping, mediated by the sizes of isovalent alkali metal impurities in Cu(I)-based semiconductors, such as copper nitride with an electron concentration of ∼1015 cm-3. Doping of isovalent Li with a smaller size to interstitial positions improves n-type conductivity, and electron concentration is controllable in the range of 1015 to 1018 cm-3. In contrast, larger isovalent Cs and Rb impurities facilitate p-type conversion, resulting in a hole concentration controllability of 1014 to 1017 cm-3. First-principles calculations indicate that Li is placed as an interstitial impurity acting as a shallow donor in conjunction with the formation of a neutral impurity on Cu defects. As the impurity size increases beyond the capacity of the vacant space, the formation of multiple acceptor-type Cu vacancies is enhanced owing to the repulsion between host Cu+ and Cs+/Rb+ impurities. Consequently, the Cs or Rb impurity is located at the sites of the N accompanied by six neighboring Cu vacancies, forming acceptor defect complexes. This size-dependent isovalent impurity doping scheme opens up an alternative avenue for advancement in optoelectronic devices using monovalent cation-based semiconductors.

Gas-Phase Structures of Fucosylated Oligosaccharides: Alkali Metal and Halogen Influences.

Fucosylated carbohydrate antigens play critical roles in physiology and pathology with function linked to their structural details. However, the separation and structural characterization of isomeric fucosylated epitopes remain challenging analytically. Here, we report for the first time the influence of alkali metal cations (Li+, Na+, K+, Rb+, and Cs+) and halogen anions (Cl-, Br-, and I-) on the gas-phase conformational landscapes of common fucosylated trisaccharides (Lewis A, X, and H types 1 and 2) and tetrasaccharides (Lewis B and Y) using trapped ion mobility spectrometry coupled to mass spectrometry and theoretical calculations. Inspection of the mobility profiles of individual standards showed a dependence on the number of mobility bands with the oligosaccharide and the alkali metal and halogen; collision cross sections are reported for all of the observed species. Results showed that trisaccharides (Lewis A, X, and H types 1 and 2) can be best mobility resolved in the positive mode using the [M + Li]+ molecular ion form (baseline resolution r ≈ 2.88 between Lewis X and A); tetrasaccharides can be best mobility resolved in the negative mode using the [M + I]- molecular ion form (baseline separation r ≈ 1.35 between Lewis B and Y). The correlation between the number of oligosaccharide conformers as a function of the molecular ion adduct was studied using density functional theory. Theoretical calculations revealed that smaller cations can form more stable structures based on the number of coordinations, while larger cations induced greater oligosaccharide reorganizations; candidate structures are proposed to better understand the gas-phase oligosaccharide rearrangement trends. Inspection of the candidate structures suggests that the interplay between ion size/charge density and molecular structure dictated the conformational preferences and, consequently, the number of mobility bands and the mobility separation across isomers. This work provides a fundamental understanding of the gas-phase structural dynamics of fucosylated oligosaccharides and their interaction with alkali metals and halogens.

Enhancing energy yield and reducing environmental impact through co-hydrothermal carbonization of undehydrated sewage sludge and fungus bran

This study presents a sustainable waste management method through co-hydrothermal carbonization (Co-HTC) of undehydrated sewage sludge (SS) and fungus bran (FB), effectively eliminating the need for additional water. The effects of the reaction severity factor (SF: 0.1, 0.2, and 0.3), the FB mixed ratio (FBMR: 0 %, 10 %, and 20 %), and the proportion of citric acid promoting agent (CAPA: 0 %, 10 %, and 20 %) on HTC performance were systematically investigated. The process was optimized for maximum energy yield (EY) using response surface methodology (RSM). The properties of the produced hydrochar, along with its EY and environmental impact, were thoroughly assessed. Results demonstrated that under optimal conditions (SF: 0.1, FBMR: 20 %, and CAPA: 20 %), EY increased by 45.84 % compared to hydrochar derived from dried SS. The dehydration and decarboxylation processes led to lower H/C and O/C ratios, producing hydrochar with reduced sulfur and nitrogen content, while the contents of alkali and alkaline earth metals, particularly calcium, increased. Furthermore, the optimized Co-HTC process had minimal environmental impact. In contrast to traditional HTC, which requires significant freshwater and involves high costs for SS drying, our innovative approach using undehydrated SS offers a cost-effective and environmentally friendly solution, paving the way for industrial-scale Co-HTC and sustainable waste valorization.

Calcium single atoms stabilized by nitrogen coordination in metal–organic frameworks as efficient solid base catalysts

Considerable attention has been paid to the preparation of single-atom solid base catalysts (SASBCs) owing to their high activity and maximized utilization of basic sites. At present, the reported fabrication methods of SASBCs, such as two-step reduction strategy and sublimation capture strategy, require high temperature. Such a high activation temperature is easy to cause the sublimation loss of alkali or alkaline earth metal atoms and destructive to the support structure. Herein, a new SASBC, Ca1/UiO-67-BPY, is fabricated, in which the alkaline earth metal Ca sites are immobilized onto N-rich metal–organic framework UiO-67-BPY at room temperature. The results show that the atomic configuration of Ca single atoms is coordinated by two N atoms in the framework. The obtained Ca SASBC possesses ordered structure and exhibits high product yield of 87.2% in the Knoevenagel reaction between benzaldehyde and malononitrile. Furthermore, thanks to the Ca single atoms sites anchored on UiO-67-BPY, the Ca1/UiO-67-BPY catalyst also shows good stability during cycles. This work might offer new insight in designing SASBCs for different base-catalyzed reactions.

2D Covalent Organic Framework Covalently Anchored with Carbon Nanotube as High-Performance Cathodes for Lithium and Sodium-Ion Batteries.

Covalent organic frameworks (COFs), featuring structural diversity, permanent porosity, and functional versatility, have emerged as promising electrode materials for rechargeable batteries. To date, amorphous polymer, COF, or their composites are mostly explored in lithium-ion batteries (LIBs), while their research in other alkali metal ion batteries is still in infancy. This can be due to the challenges that arise from large volume changes, slow diffusion kinetics, and inefficient active site utilization by the large Na+ or K+ ion. Herein, microwave-assisted imide-based 2D COF, TAPB-NDA covalently connected with amine-functionalized carbon nanotubes (TAPB-NDA@CNT) targeting the application in both Li-/Na-ion batteries, is synthesized. As-synthesized, TAPB-NDA@CNT50 displays the good performance as LIB cathode with a specific capacity of ≈138mAhg-1 at 25mAg-1, long cycling stability (81.2% retention after 2000 cycles at 300mAg-1), with excellent reversible capacity retention of ≈79.6%. Similarly, TAPB-NDA@CNT50, when employed in sodium-ion battery (SIB), exhibited 136.7mAhg-1 specific capacity at 25mAg-1, retained ≈80% of the reversible capacity after 1000 cycles at 300mAg-1 and showing excellent rate performance. The structural advantage of TAPB-NDA@CNT will encourage researchers to design COF-based cathodes for the alkali ion batteries.

Revealing the effect regularity of cations on electron storage capacity of poly(heptazine imide) in “dark photocatalysis”

As a crystalline carbon nitride material, poly(heptazine imide) (abbreviated as PHI) exhibits higher photoinduced charge separation performance than traditional melon-based carbon nitride. The excellent charge separation is mainly attributed to the fact that the photoinduced electrons can be captured by cations (such as K+ and H+) and further stored in the PHI framework with the presence of sacrificial agents (such as methanol). Due to this special property, the stored electrons can be used for delayed H2O2 or H2 production in the “dark photocatalysis” field. Nevertheless, the effect regularity of cations on the electron storage capacity of PHI is still not clear. In this work, this problem has been preliminarily revealed. The electron storage capacity of a series of PHI materials has been quantified by the H2O2 production test in dark conditions. The result indicates that the electron storage capacity of PHI samples shows a volcano curve with the alkali metal ion content. Based on experimental tests and theoretical simulations, it is concluded that the electron storage capacity of PHI is related to the conductivity of the cation and its binding force for photogenerated electrons.

Ultrahigh Pyridinic/Pyrrolic N Enabling N/S Co-Doped Holey Graphene with Accelerated Kinetics for Alkali-Ion Batteries.

Carbonaceous materials hold great promise for K-ion batteries due to their low cost, adjustable interlayer spacing, and high electronic conductivity. Nevertheless, the narrow interlayer spacing significantly restricts their potassium storage ability. Herein, hierarchical N, S co-doped exfoliated holey graphene (NSEHG) with ultrahigh pyridinic/pyrrolic N (90.6at.%) and large interlayer spacing (0.423nm) is prepared through micro-explosion assisted thermal exfoliation of graphene oxide (GO). The underlying mechanism of the micro-explosive exfoliation of GO is revealed. The NSEHG electrode delivers a remarkable reversible capacity (621 mAhg-1 at 0.05 Ag-1), outstanding rate capability (155 mAhg-1 at 10 Ag-1), and robust cyclic stability (0.005% decay per cycle after 4400 cycles at 5 Ag-1), exceeding most of the previously reported graphene anodes in K-ion batteries. In addition, the NSEHG electrode exhibits encouraging performances as anodes for Li-/Na-ion batteries. Furthermore, the assembled activated carbon||NSEHG potassium-ion hybrid capacitor can deliver an impressive energy density of 141 Whkg-1 and stable cycling performance with 96.1% capacitance retention after 4000 cycles at 1 Ag-1. This work can offer helpful fundamental insights into design and scalable fabrication of high-performance graphene anodes for alkali metal ion batteries.

Ligand‐Controlled Copper‐Catalyzed Halo‐Halodifluoromethylation of Alkenes and Alkynes Using Fluorinated Carboxylic Anhydrides

AbstractPolyhalogenated molecules are often found as bioactive compounds in nature and are used as synthetic building blocks. Fluoroalkyl compounds hold promise for the development of novel pharmaceuticals and agrochemicals, as the introduction of fluoroalkyl groups is known to improve lipophilicity, membrane permeability, and metabolic stability. Three‐component 1,2‐halo‐halodifluoromethylation reactions of alkenes are useful for their synthesis. However, general methods enabling the introduction of halodifluoromethyl (CF2X) and halogen (X’) groups in the desired combination of X and X’ are lacking. To address this gap, for the first time, we report a three‐component halo‐halodifluoromethylation of alkenes and alkynes using combinations of commercially available fluorinated carboxylic anhydrides ((CF2XCO)2O, X=Cl and Br) and alkali metal halides (X’=Cl and Br). In situ prepared fluorinated diacyl peroxides were identified as important intermediates, and the use of appropriate bipyridyl‐based ligands and a copper catalyst was essential for achieving high product selectivity. The synthetic utility of the polyhalogenated products was demonstrated by exploiting differences in the reactivities of their C−X and C−X’ bonds to achieve selective derivatization. Finally, the reaction mechanism and ligand effect were investigated using experimental and theoretical methods to provide important insights for the further development of catalytic reactions.