Dynamic Phase Transformations of Prussian Blue Analogue Crystals in Hydrotherms.

Prussian blue analogue (PBA)/metal-organic frameworks (MOFs) are multifunctional precursors for the synthesis of metal/metal compounds, carbon, and their derived composites (P/MDCs) in chemical, medical, energy, and other applications. P/MDCs combine the advantages of both the high specific surface area of PBA/MOF and the electronic conductivity of metal compound/carbon. Although the calcination under different atmospheres has been extensively studied, the transformation mechanism of PBA/MOF under hydrothermal conditions remains unclear. The qualitative preparation of P/MDCs in hydrothermal conditions remains a challenge. Here, we select PBA to construct a machine-learning model and measure its hydrothermal phase diagram. The architecture-activity relationship of substances among nine parameters was analyzed for the hydrothermal phase transformation of PBA. Excitingly, we established a universal qualitative model to accurately fabricate 31 PBA derivates. Additionally, we performed three-dimensional reconstructed transmission electron microscopy, X-ray absorption fine structure spectroscopy, ultraviolet photoelectron spectroscopy, in situ X-ray powder diffraction, and theoretical calculation to analyze the advantages of hydrothermal derivatives in the oxygen evolution reaction and clarify their reaction mechanisms. We uncover the unified principles of the hydrothermal phase transformation of PBA, and we expect to guide the design for a wide range of composites.

Oxygen Vacancy-Dependent Photocatalytic Selective Synthesis of an Unsaturated Amide on Spinel CuFe2O4.

Oxygen vacancies can change the physical and chemical properties of oxide semiconductors, which is applied to the field of ph otocatalysis, including water splitting, carbon dioxide reduction, and organic synthesis. However, the mechanism of oxygen vacancies in photocatalytic organic synthesis is still unclear. Herein, oxygen vacancies constructed on spinel CuFe2O4 nanoparticles were found to trigger the photocatalytic synthesis of an unsaturated amide with high conversion and selectivity. Such superior performance was attributed to the fact that the enriched surface oxygen vacancies could increase the charge separation efficiency and optimize the reaction path, which has been demonstrated both experimentally and theoretically.

Bifunctional monomer oligomers-based composite molecularly imprinted membranes for the electrochemical monitoring of Sudan I.

Herein, we developed a highly sensitive electrochemical sensor for the trace detection of Sudan I (SDI) dye based on composite molecularly imprinted membranes (MIMs). The pentenyl (lipoic acyl)-isoleucyl-chitosan oligosaccharide (P(L)ICO) and pentenyl-asparaginyl-chitosan oligosaccharide (PASCO) served as bifunctional monomer oligomers. After deposition of gold nanoparticles on a glassy carbon electrode (GCE) surface, a P(L)ICO layer successfully self-assembled on the surface. Subsequently, the primary MIM was polymerised on the electrode surface by using SDI as a template, PASCO as a functional monomer oligomer, and ethylene glycol dimethacrylate as a cross-linking agent. Electrochemical polymerisation was then conducted in an N,N'-methylenebisacrylamide solution. After eluting the SDI molecules from the composite MIMs, the fabricated SDI-MIM(PM)/Fn-Au/GCE demonstrated specific adsorption of SDI. Under optimal conditions, the constructed sensor exhibited a linear relationship between decreasing peak current and SDI concentration from 0.02 to 3.5 µM with a low detection limit of 4 nM (S/N = 3). As a proof of concept, SDI-MIM(PM)/Fn-Au/GCE was also applied to detect SDI in chili powder samples, with recoveries ranging from 96.8 to 106.6%.

In Situ Anchoring Polymetallic Phosphide Nanoparticles within Porous Prussian Blue Analogue Nanocages for Boosting Oxygen Evolution Catalysis.

The controllable synthesis of metal-based nanoclusters for heterogeneous catalytic reactions has received considerable attention. Nevertheless, manufacturing these architectures, while avoiding aggregation and retaining surface activity, remains challenging. Herein, for the first time we designed NiCoFe-Prussian blue analogue (PBA) nanocages as a support for in situ dispersion and anchoring of polymetallic phosphide nanoparticles (pMP-NPs). Benefiting from the porous surfaces and the synergistic effects between pMP-NPs and the cyano groups in PBA, the NiCoFe-P-NP@NiCoFe-PBA nanocages exhibit a significantly enhanced catalytic activity for oxygen evolution reaction (OER) with an overpotential of 223 mV at 10 mA cm-2 and a Tafel slope of 78 mV dec-1, outperforming the NiCoFe-PBA nanocubes, NiCoFe-P nanocages, NiFe-P-NP@NiFe-PBA nanocubes, and CoFe-P-NP@CoFe-PBA nanoboxes. This work not only offers the synthesis strategy of in situ anchoring pMP-NPs on PBA nanocages but also provides a new insight into optimized Gibbs free energy of OER by regulating electron transfer from metallic phosphides to PBA substrate.

Stepwise Li Substitution Induced Structure Evolution and Improved Nonlinear Optical Performance for Diamond-like Sulfides.

One of the key scientific issues for exploration of novel infrared nonlinear optical (NLO) crystals is to obtain ones with good hybrid NLO behaviors. Herein, we report four diamond-like Ag-based sulfides via stepwise Li substitution of Ag in Ag2ZnSnS4, including Ag2ZnSnS4 (1), (Li1.22Ag0.78)ZnSnS4 (2), (Li1.58Ag0.42)ZnSnS4 (3), and Li2ZnSnS4 (4). With the increase of Li content, the sulfide's noncentrosymmetric crystal structure changes from tetragonal I42m for 1, to orthorhombic Pmn21 for 2 and 3, and to monoclinic Pn for 4. Accordingly, their NLO responses are improved along with the increase of Li content, viz. from non-NLO-active for 1, to non-phase-matchable for 2 and 3, and to phase-matchable for 4. Their optical band gaps also increase regularly. The relationship between their chemical compositions, crystal structures, and NLO activities is investigated by means of chemical structural analysis and theoretical calculation. This work offers a new systematic case for designing promising NLO-active compounds via rarely adopted cation's stepwise partial substitution and understanding the chemical composition-structure-NLO property relationship.

Introduction of Li into Ag-Based Noncentrosymmetric Sulfides for High-Performance Infrared Nonlinear Optical Materials.

The understanding of the structure-performance relationship is beneficial to establish the balance between the second-harmonic generation (SHG) response and laser-induced damage threshold (LIDT) in exploring novel nonlinear optical (NLO) materials. In this work, a facile strategy of partial Li co-occupation with Ag is employed to investigate the structures and NLO performances of the four Ag-based noncentrosymmetric chalcogenides Ag2In2SiS6 (1), (Li0.79Ag1.21)In2SiS6 (2), (Li1.12Ag0.88)In2SiS6 (3), and (Li1.44Ag0.56)In2SiS6 (4). Both the SHG intensity and LIDT are improved as the Li element is introduced, among which 4 exhibits the optimal phase-matchable SHG response of ∼0.8 × AgGaS2 (AGS) and a high LIDT of 4 × AGS. These NLO activities are explained by theoretical calculation and the dipole moment analysis.

Synthesis, Crystal Structure, Electronic Structure, and Electrocatalytic Hydrogen Evolution Reaction of Synthetic Perryite Mineral.

Recently, it has been reported that the enstatite chondrite (EC) meteorite may contain enough hydrogen to provide a plausible explanation for water's initial existence on Earth. Perryite mineral is one of the key components of EC, but its detailed chemical composition and phase width remain elusive compared with other minerals found in EC. Therefore, we embark on a series of investigations of the synthesis, crystal structure, and electronic structure of the synthetic perryite mineral (NixFe1-x)8(TyP1-y)3 (T = Si and Ge; 1 ≥ x, y ≥ 0). Its crystal structures were established based on single-crystal and powder X-ray diffraction techniques. It is realized that its structural and phase stabilities are highly dependent on the nature of the doping element (i.e., Fe and Si). The inclusion of Si and Fe elements can greatly alter the bonding scheme near the Fermi level (Ef), which is vital to the phase stability and accounts for the chemical composition of the natural perryite mineral (quaternary compound) in EC meteorites. Furthermore, this phase exhibits good electrocatalytic activity toward the hydrogen evolution reaction (HER). The best and the worst HER performances are for the Ni8Ge2P and Ni8Si2P samples, respectively, which suggests that the long bond length and high polarity of the covalent bond are the preferred criteria to enhance the electrocatalytic HER in this series.

Enhanced Electrochemiluminescence of Porphyrin-Based Metal-Organic Frameworks Controlled via Coordination Modulation.

Precise control over the composition, morphology, and size of porphyrin-based metal-organic frameworks is challenging, but the extension of these hybrid materials will enable the creation of novel electrochemiluminescence (ECL) emitters. The coordination of various entities is made from Zn2+ ions and meso-tetra(4-carboxyphenyl)porphine (TCPP), modulated by both solvent and bathophenanthrolinedisulfonic acid disodium salt (BPS) as capping agent, resulting in limited crystal growth of Zn-TCPP in DMF/H2O (v/v, 1:1) and the formation of nanoscale TCPP-Zn-BPS. The role of BPS is also evaluated using Zn-TCPP and BPS-Zn-TCPP as controls, prepared in the absence of BPS and different coordinating sequences of ligands, respectively. The newly obtained TCPP-Zn-BPS exhibits a variety of different morphologies, as well as spectral and optoelectronic properties. The ECL behavior of TCPP-Zn-BPS is investigated by using H2O2 as co-reactant. The amplification of ECL is further studied by ECL spectroscopies and cyclic voltammetry, with the corresponding mechanism proposed.

Microporous Carbon Nanofibers Derived from Poly(acrylonitrile-co-acrylic acid) for High-Performance Supercapacitors.

Carbon nanofiber (CNF)-based supercapacitors have promising applications in the field of energy storage. It is desirable, but remains challenging, to develop CNF electrode materials with large specific surface area (SSA), high specific capacitance (SC), and high power density, as well as excellent cycling stability and high reliability. Herein, acrylonitrile-acrylic acid copolymer P(AN-co-AA) was synthesized for the preparation of nitrogen-doped microporous CNFs. Thermal degradation of the AA segment leads to the formation of micropores that are distributed not only on the CNF surface, but also inside the material. The microporous structure and nitrogen content can be manipulated at the molecular level by adjusting the weight ratio between AN and AA, and the SSA and SC could reach as high as 1099 m2 g-1 and 156 F g-1 , respectively. After KOH activation, the activated CNFs have an extremely high SSA of 2117 m2 g-1 and SC of 320 F g-1 , which are among the highest values ever reported for electric double-layer supercapacitors with an alkaline electrolyte. Furthermore, the capacitance retention, which can be maintained at 99 % even after 16 000 cyclic tests, reveals outstanding durability and repeatability.

KInSi1.32Sn0.68Se6: An Infrared Nonlinear Optical Material Containing Three Types of Tetrahedral Units.

The deficiency of nonlinear optical (NLO) materials in the infrared region pushes continuous exploration of new ones with desired performances. In this work, a novel pentanary selenide KInSi1.32Sn0.68Se6 is discovered by using a high-temperature solid-state reaction. It crystallizes in the monoclinic noncentrosymmetric space group Cc featuring a 3D [(InSi1.32Sn0.68Se6)-]n polyanionic network, and its powder sample presents promising NLO behaviors, namely 1.3-times second-harmonic generation response and close laser-induced damage threshold than those of benchmark AgGaS2. Besides, it is phase-matchable and shows a wide transparent region. Theoretical calculation addressing its electronic structure and optical property is also performed.

(Na0.60Ba0.70)Ga2Se4: An Infrared Nonlinear Optical Crystal Designed using AgGaSe2 as the Template.

A novel quaternary selenide (Na0.60Ba0.70)Ga2Se4 (1) obtained by a high-temperature method crystallizes in the non-centrosymmetric space group I4cm, and its structure features {[GaSe2]-}∞ chains. It exhibits phase-matchable second-harmonic generation responses with the largest intensity of 0.3 times that of AgGaS2, and its powder sample has a laser-induced damage threshold of ∼2.4 times that of AgGaS2. Discussion about its relationship with other highly related structures are addressed as well. Theoretical calculations are performed to analyze its electronic structure and optical properties.

Designing Sulfide Borate as a Novel Type of Second-Order Nonlinear-Optical Material.

Designing second-order nonlinear-optical (NLO) materials with new structures is an attractive topic. Here, a novel type of sulfide borate, Eu2B5O9S, and one of its derivatives combining S2-, I-, and borate anions in one structure (three in one), viz., Eu4.5(B5O9)2SI, are designed and synthesized with a high-temperature solid-state method. They crystallize in the noncentrosymmetric space group Pnn2. As the first sulfide borate being NLO-active, Eu4.5(B5O9)2SI demonstrates good NLO behavior, namely, a moderate powder NLO response of ca. 0.5 times and a high laser-induced damage threshold (LIDT) of ca. 15 times those of AgGaS2, and is phase-matchable. The design strategy and experimental results are verified and explained by density functional theory calculations.

Second-Order Nonlinear-Optical-Active Selenide Borate YSeBO2: Featuring a [YSeBO2]n Planar Belt.

Chalcogenide borates were very rarely investigated in the past. As the second selenide borate, YSeBO2 obtained by a high-temperature solid-state reaction crystallizes in the noncentrosymmetric orthorhombic space group Cmc21 with a novel structure type. Its structure consists of two basic building units, [BO3]3- planar triangles and [YO3Se4]11- pentagonal bipyramids, and features the [YSeBO2]n planar belt. Second-harmonic-generation measurement shows its phase-matchable activity. YSeBO2 has an optical energy gap of 3.45 eV. Density functional theory calculation is also performed, addressing the electronic structure and nonlinear-optical property.

Triple-Kagomé-Layer Slabs of Mixed-Valence Rare-Earth Ions Exhibiting Quantum Spin Liquid Behaviors: Synthesis and Characterization of Eu9MgS2B20O41.

We prepared a new rare-earth compound, Eu9MgS2B20O41 (EMSBO), and characterized its structural and physical properties. EMSBO consists of triple-Kagomé-layer slabs separated by nonmagnetic ions and groups. Within each slab, intervalence charge transfer has been found to occur between the Eu2+ and Eu3+ Kagomé layers, a new channel for quantum fluctuation of magnetic moments. The measured magnetic susceptibilities and the specific heat capacity exhibit very similar features characteristic of quantum spin liquid behaviors observed in other materials.

The State of Research Regarding Ordered Mesoporous Materials in Batteries.

Ordered mesoporous materials, porous materials with a pore size of 2-50 nm which are prepared via the sol-gel process using surfactant molecular aggregates as a template to assemble channels through the interfacial action of organic and inorganic substances, have recently triggered a heated debate. In addition to applications in the catalytic cracking of heavy oils and residues, the manufacturing of graft materials, the purification of water, the conversion of automobile exhaust, biochips, and the treatment of environmental pollutants via photocatalysts, ordered mesoporous materials have drawn substantial attention in the field of electrochemical energy storage due to advantages such as large specific surface area, uniform and continuously adjustable pore size, and orderly arrangement. Here, a general summary and appraisal of the study of ordered mesoporous materials for batteries in recent years is given, including the synthesis methods, meso/nanostructural features, and electrochemical capabilities of such materials.

Cu2+-Modulated in situ growth of quantum dots for split-type photoelectrochemical immunoassay of prostate-specific antigen.

A split-type photoelectrochemical immunosensor was designed for the ultrasensitive monitoring of prostate-specific antigen (PSA) based on a Cu2+-mediated catalytic reaction for inhibiting the in situ generation of CdS quantum dots (QDs) coupled with the enhancement of the CdS/MoS2 heterojunction; it was constructed by the stepwise modification of MoS2 QDs and CdS QDs onto an ITO electrode surface. In the presence of PSA, CuO NP-labeled anti-PSA antibodies were immobilized onto an anti-PSA antibody-modified 96-well plate via a sandwich immunoreaction and dissolution by hydrochloric acid to obtain a large number of Cu2+ ions. As the Cu2+-triggered catalytic oxidization of glutathione occurred, the in situ growth of CdS QDs as a signal indicator was significantly suppressed, resulting in reduction in the photocurrent response. Under optimal conditions, the biosensor exhibited desirable linearity in the range from 0.5 pg mL-1 to 10 ng mL-1, low detection limit of 0.29 pg mL-1, satisfactory selectivity, and good stability. It was applied to PSA detection in human serum, suggesting a great potential for early diagnostics of some cancers.

Transition Metal Free Monoclinic Eu8In17.33S34 and Its Anisotropic Photoelectronic Responses.

Novel Eu8In17.33S34 (1) is obtained by a solid state reaction and its structure features three parallel slabs of [In9.33S18]∞, [Eu8]∞, and [In8S16]∞, together with defects in specific lattice sites. It is the first monoclinic ternary M8- mIn18- n Q34 ( M = Pb, Sn, Eu; Q = S, Se) phase member, and the modulation from the ultralong In-S bond and lattice site with strong antibonding effect results in the unique structure feature. Its single crystals show anisotropic conductivity and photoconductivity.

Balanced Second-Order Nonlinear Optical Properties of Adducts CHI3·(S8)3 and AsI3·(S8)3: A Systematic Survey.

Two isostructural adducts CHI3·(S8)3 (1) and AsI3·(S8)3 (2) are synthesized by a simple solution method. Both of them crystallize in noncentrosymmetric R3 m, featuring van der Waals interaction linked CHI3 tetrahedra or SbI3 trigonal pyramids with crown-like S8 molecules. Both 1 and 2 show strong SHG responses and phase matchability under either 1.064 or 2.1 µm. The results of DFT calculations indicate that the electron transfer happens from S-3p to I-5p orbitals, and both of them demonstrate indirect band gaps. The NLO effects of 1 and 2 are almost fully contributed from the CHI3 or AsI3 units. Compared with AgGaS2, their powder laser damage thresholds are ca. 15 and 51 times higher.

Partial Congener Substitution Induced Centrosymmetric to Noncentrosymmetric Transformation Witnessed by K3Ga3(Ge7-xMx)Se20 (M = Si, Sn) and Their Nonlinear Optical Properties.

Crystallizing in a noncentrosymmetric (NCS) structure is the essential requirement for a crystal to be second-order nonlinear optical (NLO) active. Here, a simple strategy of partial congener substitution is introduced to induce transformation of the known centrosymmetric K3Ga3Ge7Se20 (P21/c) to the new isostructural NCS species K3Ga3(Ge6.17Sn0.83)Se20 (1) and K3Ga3(Ge4.95Si2.05)Se20 (2) (Pc). Their structures feature a {[Ga3(Ge7-xMx)Se20]3-}∞ (M = Si, Sn) polyanionic framework built from the basic functional motif M'Se4 (M' = Ga, Ge, M) tetrahedra, similar to but slightly distorted from that of K3Ga3Ge7Se20. Their NCS structures are verified by the NLO activities. The NLO response of 1 is ∼1/3 times that of the benchmark AgGaS2 under a 2.1 µm laser radiation, while 2 exhibits a weak effect, and both are NLO phase-matchable. Their optical band gaps are measured to be 2.02 and 2.12 eV, and they are transparent in the ranges of 0.61-25 and 0.58-25 µm, respectively.

A nanocomposite prepared from hemin and reduced graphene oxide foam for voltammetric sensing of hydrogen peroxide.

A foam consisting of reduced graphene oxide was synthesized by a one-pot hydrothermal method. The foam was used to prepare a nanocomposite with hemin which is formed via π-interactions. The nanocomposite was incorporated via a Nafion film and then placed on a glassy carbon electrode (GCE). The modified GCE displays outstanding catalytic activity towards H2O2. It is assumed that this is due to (a) the redox-active center [Fe(III/II)] of hemin, and (b) the crosslinked macroporous structure of the foam. Both improve the electron transfer rate and electrochemical signals. Under the optimum experimental conditions and a working voltage of typically -0.41 mV (vs. SCE), the sensor has a 2.8 nM H2O2 detection limit, and the analytically useful range extends from 5 nM to 5 mM with a sensitivity of 50.5 µA µM-1 cm-2. The modified GCE has high sensitivity and fast response. It was utilized to quantify H2O2 in spiked environmental water samples. Graphical abstractSchematic representation of the electrochemical sensor based on a nanocomposite prepared from hemin and reduced graphene oxide foam, which can be applied to the determination of hydrogen peroxide in serum.