Dual Ion Co-insertion Induced Spontaneous and Reversible Phase Conversion Chemistry for Unprecedented Zn2+ Storage.

Prussian blue analogues are highly promising electrode materials due to their versatile electrochemical activity and low cost. However, they often suffer from severe structural damage caused by the Jahn-Teller distortion and dissolution of high-spin outer metal ions, resulting in poor cycle life. Material modification and electrolyte regulation have been the common approaches to address this issue, albeit with very limited success. We report here a novel and efficient strategy to preserve structural stability by co-inserting Co2+ and Zn2+ ions in KCo[Fe(CN)6]. This co-insertion induced a spontaneous and reversible phase conversion by the replacement of low-spin inner ion (Fe3+), which efficiently relieves structural damage caused by Jahn-Teller distortion and metal-ion dissolution, leading to an outstanding Zn2+ storage capacity and an exceptional improvement of cycle life with a capacity retention of 97.7% over 4400 cycles at 40 C. We also demonstrated the enhancement of co-intercalation on ion migration using a combined approach of experimental and density functional theory (DFT) calculations. This work provides an important progress to solve the cycle stability of Prussian blue analogues towards their practical application as electrode materials for aqueous batteries.

Boosting the "Solid-Liquid-Solid" Conversion Reaction via Bifunctional Carbonate-Based Electrolyte for Ultra-long-life Potassium-Sulfur Batteries.

Potassium-sulfur (K-S) batteries have attracted wide attention owing to their high theoretical energy density and low cost. However, the intractable shuttle effect of K polysulfides results in poor cyclability of K-S batteries, which severely limits their practical application. Herein, a bifunctional concentrated electrolyte (3 mol L-1 potassium bis(trifluoromethanesulfonyl)imide in ethylene carbonate (EC)) with high ionic conductivity and low viscosity is developed to regulate the dissolution behavior of polysulfides and induce uniform K deposition. The organic groups in the cathode electrolyte interphase layer derived from EC can effectively block the polysulfide shuttle and realize a "solid-liquid-solid" reaction mechanism. The KF-riched solid-electrolyte interphase inhibits K dendrite growth during cycling. As a result, the achieved K-S batteries display a high reversible capacity of 654 mAh g-1 at 0.5 A g-1 after 800 cycles and a long lifespan over 2000 cycles at 1 A g-1 .

Phase Conversion Accelerating "Zn-Escape" Effect in ZnSe-CFs Heterostructure for High Performance Sodium-Ion Half/Full Batteries.

Sodium-ion batteries (SIBs) are considered as a promising large-scale energy storage system owing to the abundant and low-cost sodium resources. However, their practical application still needs to overcome some problems like slow redox kinetics and poor capacity retention rate. Here, a high-performance ZnSe/carbon fibers (ZnSe-CFs) anode is demonstrated with high electrons/Na+ transport efficiency for sodium-ion half/full batteries by engineering ZnSe/C heterostructure. The electrochemical behavior of the ZnSe-CFs heterostructure anode is deeply studied via in situ characterizations and theoretical calculations. Phase conversion is revealed to accelerate the "Zn-escape" effect for the formation of robust solid electrolyte interphase (SEI). This leads to the ZnSe-CFs delivering a superior rate performance of 206 mAh g-1 at 1500 mA g-1 for half battery and an initial discharge capacity of 197.4 mAh g-1 at a current density of 1 A g-1 for full battery. The work here heralds a promising strategy to synthesize advanced heterostructured anodes for SIBs, and provides the guidance for a better understanding of phase conversion anodes.

Phase Control of Cs-Pb-Br Derivatives to Suppress 0D Cs4 PbBr6 for High-Efficiency and Stable All-Inorganic CsPbBr3 Perovskite Solar Cells.

The precise phase control of Cs-Pb-Br derivatives from 3D CsPbBr3 to 0D Cs4 PbBr6 highly determines the photovoltaic performance of all-inorganic CsPbBr3 perovskite solar cells (PSCs). Herein, the preferred phase conversion from precursor to Cs-Pb-Br derivatives is revealed by theoretically calculating the Gibbs free energies (∆G) of various phase conversion processes, allowing for a simplified multi-step solution-processable spin-coating method to hinder the formation of detrimental 0D Cs4 PbBr6 phase and enhance the photovoltaic performance of a PSC because of its large exciton binding energy, which is regarded as a recombination center. By further accelerating the interfacial charge extraction with a novel 2D transition metal dichalcogenide ReSe2 , the hole-free CsPbBr3 PSC achieves a champion efficiency of 10.67% with an impressive open-circuit voltage of 1.622 V and an excellent long-term stability. This work provides an in-depth understanding on the precise Cs-Pb-Br perovskite phase control and the effect of derivatives on photovoltaic performance of advanced CsPbBr3 PSCs.

A Solid-Phase Conversion Sulfur Cathode with Full Capacity Utilization and Superior Cycle Stability for Lithium-Sulfur Batteries.

Solid phase conversion sulfur cathode is an effective strategy for eliminating soluble polysulfide intermediates (LiPSs) and improving cyclability of Li-S batteries. However, realizing such a sulfur cathode with high sulfur loading and high capacity utilization is very challenging due to the insulating nature of sulfur. In this work, a strategy is proposed for fabricating solid phase conversion sulfur cathode by encapsulating sulfur in the mesoporous channels of CMK-3 carbon to form a coaxially assembled sulfur/carbon (CA-S/C) composite. Vinyl carbonate (VC) is simultaneously utilized as the electrolyte cosolvent to in-situ form a dense solid electrolyte interface (SEI) on the CA-S/C composite surface through its nucleophilic reaction with the freshly generated polysulfides at the beginning of initial discharge, thus separating the direct contact of interior sulfur with the outer electrolyte. As expected, such a CA-S/C cathode can operate in a solid phase conversion manner in the VC-ether cosolvent electrolyte to exhibit a full capacity utilization (1667 mA h g-1 , ≈100%), a high rate capability of 2.0 A g-1 and excellent long-term cyclability over 500 cycles even at a high sulfur loading (75%, based on the weight of CA-S/C composite), demonstrating great promise for constructing high-energy-density and cycle-stable Li-S batteries.

Rational Electrolyte Design toward Cyclability Remedy for Room-Temperature Sodium-Sulfur Batteries.

Rechargeable room-temperature sodium-sulfur (RT Na-S) batteries are a promising energy storage technology, owing to the merits of high energy density and low cost. However, their electrochemical performance has been severely hindered by the poor compatibility between the existing electrolytes and the electrodes. Here, we demonstrate that an all-fluorinated electrolyte, containing 2,2,2-trifluoro-N,N-dimethylacetamide (FDMA) solvent, 1,1,2,2-tetrafluoroethyl methyl ether (MTFE) anti-solvent and fluoroethylene carbonate (FEC) additive, can greatly enhance the reversibility and cyclability of RT Na-S batteries. A NaF- and Na3 N-rich cathode electrolyte interphase derived from FDMA and FEC enables a "quasi-solid-phase" Na-S conversion, eliminating the shuttle of polysulfides. The MTFE not only reduces polysulfide dissolution, but also further stabilizes the Na anode via a tailored solvation structure. The as-developed RT Na-S batteries deliver a high capacity, long lifespan, and enhanced safety.

Precise Phase Control of Large-Scale Inorganic Perovskites via Vapor-Phase Anion-Exchange Strategy.

Anion exchange offers great flexibility and high precision in phase control, compositional engineering, and optoelectronic property tuning. Different from previous successful anion exchange process in liquid solution, herein, a vapor-phase anion-exchange strategy is developed to realize the precise phase and bandgap control of large-scale inorganic perovskites by using gas injection cycle, producing some perovskites such as CsPbCl3 which has never been reported in thin film morphology. Ab initio calculations also provide the insightful mechanism to understand the impact of anion exchange on tuning the electronic properties and optimizing the structural stability. Furthermore, because of precise control of specific atomic concentrations, intriguing tunable photoluminescence is observed and photodetectors with tunable photoresponse edge from green to ultraviolet light can be realized accurately with an ultrahigh spectral resolution of 1 nm. Therefore, a new, universal vapor-phase anion exchange method is offered for inorganic perovskite with fine-tunable optoelectronic properties.

EDTA-assisted phase conversion synthesis of (Gd0.95RE0.05)PO4 nanowires (RE = Eu, Tb) and investigation of photoluminescence.

Hexagonal (Gd0.95RE0.05)PO4·nH2O nanowires ~300 nm in length and ~10 nm in diameter have been converted from (Gd0.95RE0.05)2(OH)5NO3·nH2O nanosheets (RE = Eu, Tb) in the presence of monoammonium phosphate (NH4H2PO4) and ethylene diamine tetraacetic acid (EDTA). They were characterized by X-ray diffraction, thermogravimetry, electron microscopy, and Fourier transform infrared and photoluminescence spectroscopies. It is shown that EDTA played an essential role in the morphology development of the nanowires. The hydrothermal products obtained up to 180 °C are of a pure hexagonal phase, while monoclinic phosphate evolved as an impurity at 200 °C. The nanowires undergo hexagonal→monoclinic phase transformation upon calcination at ≥600 °C to yield a pure monoclinic phase at ~900 °C. The effects of calcination on morphology, excitation/emission, and fluorescence decay kinetics were investigated in detail with (Gd0.95Eu0.05)PO4 as example. The abnormally strong 5D0→7F4 electric dipole Eu3+ emission in the hexagonal phosphates was ascribed to site distortion. The process of energy migration was also discussed for the optically active Gd3+ and Eu3+/Tb3+ ions.

Influence of Coformer Stoichiometric Ratio on Pharmaceutical Cocrystal Dissolution: Three Cocrystals of Carbamazepine/4-Aminobenzoic Acid.

Cocrystallization is a technique to optimize solid forms that shows great potential to improve the solubility of active pharmaceutical ingredients (APIs). In some systems, an API can form cocrystals in multiple stoichiometries with the same coformer. However, it remains unclear how coformer stoichiometry influences solubility. This paper investigates the pharmaceutical:coformer pair carbamazepine (CBZ)/p-aminobenzoic acid (PABA); both CBZ/PABA 1:1 and 2:1 cocrystals are known, and a novel 4:1 CBZ/PABA cocrystal is reported here. The 4:1 cocrystal is structurally characterized, and phase stability data suggest that it is a thermodynamically unstable form. Dissolution experiments show that there is no correlation between the cocrystal stoichiometry and dissolution rate in this system. On the other hand, with the relatively weak intermolecular interactions, metastable forms can be beneficial to dissolution rate, which suggests that more effort should be devoted to cocrystal production with kinetic growth methods.

Measurement of permanganate index in environmental water via indirect phase-conversion strategy.

In this work, we proposed an indirect phase-conversion strategy to construct a new approach for accurately and efficiently determining the permanganate index in water samples via headspace GC measurement. After the reducible substances in water reacted with excess potassium permanganate, the remaining potassium permanganate underwent a reaction with sodium oxalate under acidic conditions. The carbon dioxide generated from the gas-evolving reaction was then analyzed by headspace GC. Our findings showed that this new approach boasts high precision (relative standard deviation ≤ 2.18%) and accuracy for permanganate index analysis, thus validating the effectiveness of this new method in analyzing permanganate index. The introduction of the indirect phase-conversion strategy in this study is expected to set a precedent for further advancements in methodologies designed to indirectly evaluate substances capable of undergoing gas-producing reactions.

Quantifying sodium hypochlorite content in hypochlorite-based disinfectants via phase-conversion headspace technique.

In this work, a novel and efficient approach for sodium hypochlorite analysis is proposed via phase-conversion headspace technique, which is based on the gas chromatography (GC) detection of generated carbon dioxide (CO2) from the redox reaction of sodium hypochlorite with sodium oxalate. The data obtained by the proposed method suggest the high detecting precision and accuracy. In addition, the method has low detection limits (limit of quantification (LOQ) = 0.24 µg/mL), and the recoveries of added standard ranged from 98.33 to 101.27 %. The proposed phase-conversion headspace technique is efficient and automated, thereby offering an efficient strategy for highly efficient analysis of sodium hypochlorite and related products.

Boosting Charge Transport and Catalytic Performance in MoS2 by Zn2+ Intercalation Engineering for Lithium-Sulfur Batteries.

Transition metal dichalcogenides (TMDs) have been widely studied as catalysts for lithium-sulfur batteries due to their good catalytic properties. However, their poor electronic conductivity leads to slow sulfur reduction reactions. Herein, a simple Zn2+ intercalation strategy was proposed to promote the phase transition from semiconducting 2H-phase to metallic 1T-phase of MoS2. Furthermore, the Zn2+ between layers can expand the interlayer spacing of MoS2 and serve as a charge transfer bridge to promote longitudinal transport along the c-axis of electrons. DFT calculations further prove that Zn-MoS2 possesses better charge transfer ability and stronger adsorption capacity. At the same time, Zn-MoS2 exhibits excellent redox electrocatalytic performance for the conversion and decomposition of polysulfides. As expected, the lithium-sulfur battery using Zn0.12MoS2-carbon nanofibers (CNFs) as the cathode has high specific capacity (1325 mAh g-1 at 0.1 C), excellent rate performance (698 mAh g-1 at 3 C), and outstanding cycle performance (it remains 604 mAh g-1 after 700 cycles with a decay rate of 0.045% per cycle). This study provides valuable insights for improving electrocatalytic performance of lithium-sulfur batteries.

Thermodynamic and structural relationships between the two polymorphs of 1,3-dimethylurea.

The title compound exists as polymorph (I), Fdd2 with Z = 8 [Pérez-Folch et al. (1997). J. Chem. Cryst. 27, 367-369; Marsh (2004). Acta Cryst. B60, 252-253], and as polymorph (II), P2(1)2(1)2 with Z = 2 [Martins et al. (2009). J. Phys. Chem. A, 113, 5998-6003]. We have redetermined both structures at somewhat lower temperatures [(I) at 180 K rather than room temperature; (II) at 100 K rather than 150 K]. For polymorph (I) the space group Fdd2 is confirmed rather than the original choice of Cc. The molecular structures of both polymorphs are essentially identical, with exact crystallographic twofold symmetry, approximate C(2v) symmetry, and a trans orientation of the H-N-C=O moiety. In both polymorphs the molecules associate into chains of rings with graph set C(4)[R(2)(1)(6)] via bifurcated hydrogen-bond systems C(N-H)(2)···O=C. In the polar structure (I) the chains are necessarily all parallel, whereas in (II) equal numbers of parallel and antiparallel chains are present. Further physical investigations [differential scanning calorimetry (DSC), powder investigations, solvent-induced phase conversions] were undertaken: these showed: (i) that the commercially available compound consists predominantly of polymorph (II), which on heating transforms into polymorph (I) by an endothermic reaction, so that both polymorphs are related by enantiotropism; (ii) that polymorph (I) represents the more stable modification at room temperature, where polymorph (II) is metastable, with the thermodynamic transition temperature lying somewhere between 253 K and room temperature. An apparent third polymorph, consisting of fibrous needles, was shown by powder diffraction to consist of a mixture of polymorphs (I) and (II).

Routes to Electrochemically Stable Sulfur Cathodes for Practical Li-S Batteries.

Lithium-sulfur (Li-S) batteries have been investigated intensively as a post-Li-ion technology in the past decade; however, their realizable energy density and cycling performance are still far from satisfaction for commercial development. Although many extremely high-capacity and cycle-stable S cathodes and Li anodes are reported in literature, their use for practical Li-S batteries remains challenging due to the huge gap between the laboratory research and industrial applications. The laboratory research is usually conducted by use of a thin-film electrode with a low sulfur loading and high electrolyte/sulfur (E/S) ratios, while the practical batteries require a thick/high sulfur loading cathode and a low E/S ratio to achieve a desired energy density. To make this clear, the inherent problems of dissolution/deposition mechanism of conventional sulfur cathodes are analyzed from the viewpoint of polarization theory of porous electrode after a brief overview of the recent research progress on sulfur cathodes of Li-S batteries, and the possible strategies for building an electrochemically stable sulfur cathode are discussed for practically viable Li-S batteries from the authors' own understandings.

Realizing of ZSM-5 microspheres with enhanced catalytic properties prepared from iron ore tailings via solid-phase conversion method.

The comprehensive utilization of iron ore tailings (IOTs) not only resolved environmental problems but also brought huge economic benefits. In this study, the synthetic route presented herein provides a novel method for the synthesis of ZSM-5 microspheres from IOTs. The effects of Si/Al molar ratios and the pH of the precursor solution on the formation of zeolite was evaluated by various analytical methods. The catalytic performance of the catalyst prepared by the solid-phase conversion method (denoted as MP-ZSM-5) was evaluated by methanol-to-propylene (MTP) reaction. Compared with the zeolite catalyst that synthesized via the conventional hydrothermal method (denoted as HM-ZSM-5), MP-ZSM-5 not only prolongs catalytic lifetime from 18.7 to 36.0 h but also has higher selectivity for propylene by MP-ZSM-5 (43.7%) than that for HM-ZSM-5 (38.6%). In addition, Kissinger-Akahira-Sunose (KAS) model is applied to the TG result to study the template removal process kinetics. The average activation energy values required for the removal of CTAB and TPABr are 201.11 ± 13.42 and 326.88 ± 16.91 kJ∙mol-1, respectively. Furthermore, this result is well coupled with the model-free kinetic algorithms to determine the conversion and isoconversion of the TPABr and CTAB decomposition in ZSM-5, which serves as important guidelines for the industrial production process.

Recovering metals from flue dust produced in secondary copper smelting through a novel process combining low temperature roasting, water leaching and mechanochemical reduction.

Flue dust from secondary copper smelting (FDSC) is a hazardous waste as well as a secondary resource due to the high content of Cl, Br, and valuable metals (Pb, Cu, Zn, Cd). Herein, a novel process, combined low-temperature roasting, water leaching, and mechanochemical reduction, was developed for recovering metals from the FDSC. The phase conversion and behavior of the main elements in the whole process were explored based on thermodynamic analysis, experimental research, and various characterization. First, thermodynamics calculation revealed that adding H2SO4 could significantly decrease the roasting temperature and promote the generation of soluble metal sulfates. The experimental results showed that more than 99% of Cl and Br were removed by roasting at 325 °C and 1.5 times H2SO4 addition. Subsequently, the Cu, Zn, and Cd were almost completely leached by water under the conditions of 80 â„ƒ, 2 h and L/S = 5 mL·g-1, while Pb was rejected and enriched in the residue. Finally, using iron powder as a reductant, 96.7% of PbSO4 was reduced to elemental lead at room temperature with the aid of mechanical force. The findings illustrated that the recovery performance of metals and environmental benefits will be greatly improved by the proposed process.

Sequential Phase Conversion-Induced Phosphides Heteronanorod Arrays for Superior Hydrogen Evolution Performance to Pt in Wide pH Media.

Developing an efficient and non-precious pH-universal hydrogen evolution reaction electrocatalyst is highly desirable for hydrogen production by electrochemical water splitting but remains a significant challenge. Herein, a hierarchical structure composed of heterostructured Ni2 P-Ni12 P5 nanorod arrays rooted on Ni3 S2 film (Ni2 P-Ni12 P5 @Ni3 S2 ) via a simultaneous corrosion and sulfidation is built followed by a phosphidation treatment toward the metallic nickel foam. The combination of theoretical calculations with in/ex situ characterizations unveils that such a unique sequential phase conversion strategy ensures the strong interfacial coupling between Ni2 P and Ni12 P5 as well as the robust stabilization of 1D heteronanorod arrays by Ni3 S2 film, resulting in the promoted water adsorption/dissociation energy, the optimized hydrogen adsorption energy, and the enhanced electron/proton transfer ability accompanied with an excellent stability. Consequently, Ni2 P-Ni12 P5 @Ni3 S2 /NF requires only 32, 46, and 34 mV overpotentials to drive 10 mA cm-2 in 1.0 m KOH, 0.5 m H2 SO4 , and 1.0 m phosphate-buffered saline electrolytes, respectively, exceeding almost all the previously reported non-noble metal-based electrocatalysts. This work may pave a new avenue for the rational design of non-precious electrocatalysts toward pH-universal hydrogen evolution catalysis.

Dissolution-Precipitation Synthesis and Characterization of Zinc Whitlockite with Variable Metal Content.

In the present work, a series of zinc whitlockite (CaxZny(HPO4)2(PO4)12) powders was synthesized by a low-temperature dissolution-precipitation process for the first time. The phase conversion from calcium hydroxyapatite to zinc whitlockite occurred in an acidic medium in the presence of Zn2+ ions. Variable chemical composition of the synthesis products was achieved by changing Ca-to-Zn molar ratio in the reaction mixture. Investigation of the phase evolution as a function of time demonstrated that phase-pure zinc whitlockite powders can be synthesized in just 3 h. It is also demonstrated that single-phase products can be obtained when the Ca-to-Zn ratio in the reaction medium is in the range from 9 to 30. With higher or lower ratios, neighboring crystal phases such as scholzite or calcium hydroxyapatite were obtained. The morphology of the synthesized powders was found to be dependent on the chemical composition, transforming from hexagonal to rhombohedral plates with the increase of Zn content. Thermal stability studies revealed that the synthesized compounds were thermally unstable and decomposed upon heat treatment.

Graphdiyne-like Porous Organic Framework as a Solid-Phase Sulfur Conversion Cathodic Host for Stable Li-S Batteries.

As a unique branch of Li-S batteries, solid-phase sulfur conversion polymer cathodes have shown superior stability with fast ion-transfer kinetics and high discharge capacities owing to the mere existence of short-chain sulfur species during charging/discharging. However, representative compounds such as sulfurized polyacrylonitrile (SPAN) and polyaniline (SPANI) suffer from low sulfur contents and poor cycling performances under large current densities due to the sulfurization occurring only on polymers' surface. Here, a graphdiyne-like porous organic framework, denoted as GPOF, is synthesized and used as a host for enabling solid-phase sulfur conversion. Plenty of unsaturated bonds in GPOF provide sufficient reaction sites to bind sulfur chains, resulting in a high active sulfur content in the cathode. Moreover, the microporous GPOF possesses suitable cavities to accommodate the volume expansion, leading to favorable long-term cycling stability. As a result, the sulfurized GPOF cathode (SGPOF-320) displays outstanding electrochemical stability with negligible capacity decline after 250 cycles at 0.2 C with an average discharge capacity of 925 mA h g-1. Our work applies a facile procedure to produce sulfur conversion porous polymer cathodes, which could provide a proper way for exploring more suitable cathode materials for high-performance Li-S batteries.

Millisecond Conversion of Metastable 2D Materials by Flash Joule Heating.

Controllable phase engineering is vital for precisely tailoring material properties since different phase structures have various electronic states and atomic arrangements. Rapid synthesis of thermodynamically metastable materials, especially two-dimensional metastable materials, with high efficiency and low cost remains a large challenge. Here we report flash Joule heating (FJH) as an electrothermal method to achieve the bulk conversion of transition metal dichalcogenides, MoS2 and WS2, from 2H phases to 1T phases in milliseconds. The conversions can reach up to 76% of flash MoS2 using tungsten powder as conductive additive. Different degrees of phase conversion can be realized by controlling the FJH conditions, such as reaction duration and additives, which allows the study of ratio-dependent properties. First-principles calculations confirm that structural processes associated with the FJH, such as vacancy formation and charge accumulation, result in stabilization of the 1T phases. FJH offers rapid access to bulk quantities of the hitherto hard-to-access 1T phases, a promising method for further fundamental research and diverse applications of metastable phases.