Additive-Enhanced Crystallization of Inorganic Perovskite Single Crystals for High-Sensitivity X-Ray Detection

Inorganic cesium lead halide perovskite single crystals are particularly intriguing to ionizing radiation detection by virtue of their material stability and high attenuation coefficients. However, the growth of high-quality inorganic perovskite single crystals remains challenging, mainly due to the limited solubility. In this work, an additive-enhanced crystallization method is proposed for cesium lead perovskites. The additive can remarkably increase the solubility of cesium bromide in dimethyl sulfoxide (DMSO) forming a balanced stoichiometric precursor solution, which prevents the formation of impurity phases. In addition, the additives would react with DMSO generating glyoxylic acid (GLA) via nucleophilic substitution and Kornblum oxidation reactions. The GLA can form stable PbBr₂-DMSO-GLA complexes, which enables better crystallinity, uniformity and much longer carrier lifetimes for the grown single crystals. The X-ray detectors using the additive-enhanced crystals exhibit an ultra-high sensitivity of 3.0 × 10⁴ µC Gy_air⁻¹ cm⁻² which is more than two orders of magnitude higher than that for the control devices.     

Metal-Free Halide Perovskite Single Crystals with Very Long Charge Lifetimes for Efficient X-ray Imaging

Metal-free halide perovskites, as a specific category of the perovskite family, have recently emerged as novel semiconductors for organic ferroelectrics and promise the wide chemical diversity of the ABX₃ perovskite structure with mechanical flexibility, light weight, and eco-friendly processing. However, after the initial discovery 17 years ago, there has been no experimental information about their charge transport properties and only one brief mention of their optoelectronic properties. Here, growth of large single crystals of metal-free halide perovskite DABCO-NH₄Br₃ (DABCO = N-N′-diazabicyclo[2.2.2]octonium) is reported together with characterization of their instrinsic optical and electronic properties and demonstration, of metal-free halide perovskite optoelectronics. The results reveal that the crystals have an unusually large semigap of ≈16 eV and a specific band nature with the valence band maximum and the conduction band minimum mainly dominated by the halide and DABCO²⁺, respectively. The unusually large semigap rationalizes extremely long lifetimes approaching the millisecond regime, leading to very high charge diffusion lengths (tens of μm). The crystals also exhibit high X-ray attenuation as well as being lightweight. All these properties translate to high-performance X-ray imaging with sensitivity up to 173 μC Gy_air⁻¹ cm⁻². This makes metal-free perovskites novel candidates for the next generation of optoelectronics.     

Periodate-Based Perovskite Energetic Materials: A Strategy for High-Energy Primary Explosives

The requirements for high energy and green primary explosives are more and more stringent because of the rising demand in the application of micro initiation explosive devices. Four new energetic compounds with powerful initiation ability are reported and their performances are experimentally proven as designed, including non-perovskites ([H₂DABCO](H₄IO₆)₂·2H₂O, named TDPI-0) and perovskitoid energetic materials (PEMs) ([H₂DABCO][M(IO₄)₃]; DABCO=1,4-Diazabicyclo[2.2.2]octane, M=Na⁺, K⁺, and NH₄⁺ for TDPI-1, -2, and -4, respectively). The tolerance factor is first introduced to guide the design of perovskitoid energetic materials (PEMs). In conjunction with [H₂DABCO](ClO₄)₂·H₂O (DAP-0) and [H₂DABCO][M(ClO₄)₃] (M=Na⁺, K⁺, and NH₄⁺ for DAP-1, -2, and -4), the physiochemical properties of the two series are investigated between PEMs and non-perovskites (TDPI-0 and DAP-0). The experimental results show that PEMs have great advantages in improving the thermal stability, detonation performance, initiation capability, and regulating sensitivity. The influence of X-site replacement is illustrated by hard–soft-acid–base (HSAB) theory. Especially, TDPIs possess much stronger initiation capability than DAPs, which indicates that periodate salts are in favor of deflagration-to-detonation transition. Therefore, PEMs provide a simple and feasible method for designing advanced high energy materials with adjustable properties.     

Neutron flux measurements with a Li2B4O7 crystal

The effect of neutron irradiation on a lithium tetraborate (Li₂B₄O₇, LBO) single crystal has been investigated. The crystals of high optical quality are found to be quite stable under high neutron fluence. This study shows that LBO crystals can be used as a proportional counter for neutron fluxes of the order 10⁹ cm⁻² s⁻¹ and higher. The detectors fabricated were found to have a sensitivity of ∼3×10⁻¹⁸ A (nv)⁻¹.     

Dinitrogen Reduction Coupled with Methanol Oxidation for Low Overpotential Electrochemical NH3 Synthesis Over Cobalt Pyrophosphate as Bifunctional Catalyst

Electrochemical dinitrogen (N₂) reduction to ammonia (NH₃) coupled with methanol electro-oxidation is presented in the current work. Here, methanol oxidation reaction (MOR) is proposed as an alternative anode reaction to oxygen evolution reaction (OER) to accomplish electrons-induced reduction of N₂ to NH₃ at cathode and oxidation of methanol at anode in alkaline media thereby reducing the overall cell voltage for ammonia production. Cobalt pyrophosphate micro-flowers assembled by nanosheets are synthesized via a surfactant-assisted sonochemical approach. By virtue of structural and morphological advantages, the maximum Faradaic efficiency of 43.37% and NH₃ yield rate of 159.6 µg h⁻¹ mg_ca⁻¹ is achieved at a potential of −0.2 V versus RHE. The proposed catalyst is shown to also exhibit a very high activity (100 mA mg⁻¹ at 1.48 V), durability (2 h) and production of value-added formic acid at anode (2.78 µmol h⁻¹ mg_cat⁻¹ and F.E. of 59.2%). The overall NH₃ synthesis is achieved at a reduced cell voltage of 1.6 V (200 mV less than NRR-OER coupled NH₃ synthesis) when OER at anode is replaced with MOR and a high NH₃ yield rate of 95.2 µg h⁻¹ mg_cat⁻¹ and HCOOH formation rate of 2.53 µmol h⁻¹ mg⁻¹ are witnessed under full-cell conditions.     

Electronic-Grade High-Quality Perovskite Single Crystals by a Steady Self-Supply Solution Growth for High-Performance X-ray Detectors

High-quality perovskite single crystals with large size are highly desirable for the fundamental research and high energy detection application. Here, a simple and convenient solution method, featuring continuous-mass transport process (CMTP) by a steady self-supply way, is shown to keep the growth of semiconductor single crystals continuously stable at a constant growth rate until an expected crystal size is achieved. A significantly reduced full width at half-maximum (36 arcsec) of the (400) plane from the X-ray rocking curve indicates a low angular dislocation of 6.8 × 10⁶ cm⁻² and hence a higher crystalline quality for the CH₃NH₃PbI₃(MAPbI₃) single crystals grown by CMTP as compared to the conventional inverse temperature crystallization (ITC) method. Furthermore, the CMTP-based single crystals have lower trap density, reduced by nearly 200% to 4.5 × 10⁹ cm⁻³, higher mobility increased by 187% to 150.2 cm² V⁻¹ s⁻¹, and higher mobility–lifetime product increased by around 450% to 1.6 × 10⁻³ cm² V⁻¹, as compared with the ITC-grown reference sample. The high performance of the CMTP-based MAPbI₃ X-ray detector is comparable to that of a traditional high-quality CdZnTe device, indicating the CMTP method as being a cost-efficient strategy for high-quality electronic-grade semiconductor single crystals.     

Defective TiO2−x for High-Performance Electrocatalytic NO Reduction toward Ambient NH3 Production

Synthesis of green ammonia (NH₃) via electrolysis of nitric oxide (NO) is extraordinarily sustainable, but multielectron/proton-involved hydrogenation steps as well as low concentrations of NO can lead to poor activities and selectivities of electrocatalysts. Herein, it is reported that oxygen-defective TiO₂ nanoarray supported on Ti plate (TiO_2−x/TP) behaves as an efficient catalyst for NO reduction to NH₃. In 0.2 m phosphate-buffered electrolyte, such TiO_2−x/TP shows competitive electrocatalytic NH₃ synthesis activity with a maximum NH₃ yield of 1233.2 µg h⁻¹ cm⁻² and Faradaic efficiency of 92.5%. Density functional theory calculations further thermodynamically faster NO deoxygenation and protonation processes on TiO_2−x (101) compared to perfect TiO₂ (101). And the low energy barrier of 0.7 eV on TiO_2−x (101) for the potential-determining step further highlights the greatly improved intrinsic activity. In addition, a Zn-NO battery is fabricated with TiO_2−x/TP and Zn plate to obtain an NH₃ yield of 241.7 µg h⁻¹ cm⁻² while providing a peak power density of 0.84 mW cm⁻².     

Charge-Assisted Hydrogen-Bonded Organic Frameworks with Inorganic Ammonium Regulated Switchable Open Polar Sites

Surface open polar sites within the voids of porous molecular crystals define the localized physicochemical environment for critical functions such as gas separation and molecular recognition. This study presents a new charge-assisted hydrogen bonding (H-bonding) motif, by exploiting inorganic ammonium (NH₄⁺) cations as H-bond donors, to regulate the assembly of C₂-symmetric carboxylic tectons for building robust H-bonded frameworks with permanent ultra-micropores and open oxygen sites. Diverse building blocks are bridged by tetrahedral NH₄⁺ to expand distinctive H-bonded networks with varied pore architectures. Particularly, the open polar oxygen sites can be switched by altering NH₄⁺ sources to tune the deprotonation of carboxyl-containing tectons. The activated porous PTBA·NH₄·DMF preserves the pore architecture and open polar oxygen sites, exhibiting remarkably selective sorption of CO₂ (107.8 cm³ g⁻¹,195 K) over N₂ (11.2 cm³ g⁻¹, 77 K) and H₂ (1.4 cm³ g⁻¹, 77 K).     

Valence Engineering Enhancing NH4+ Storage Capacity of Manganese Oxides

Ammonium ions (NH₄⁺), as non-metallic charge carriers, are attracting attention in aqueous batteries due to its low molar mass, element sufficiency, and non-toxicity. However, the host materials for NH₄⁺ storage are still limited. Herein, an oxygen defects-rich manganese oxide (MnO_2–x) for NH₄⁺ storage are reported. The oxygen defects can endow the MnO_2–x sample with improved electric conductivity and low interface activation energy. The electrochemical reaction mechanism is also verified by using ex situ X-ray photoelectron spectroscopy (XPS) and fourier transform infrared spectroscopy (FT-IR), demonstrating the insertion and extraction of NH₄⁺ in the MnO_2–x by formation/breaking of a hydrogen bond. As a result, MnO_2–x delivers a high capacity of 109.9 mAh g⁻¹ at the current density of 0.5 A g⁻¹ and retention of 24 mAh g⁻¹ after 1000 cycles at the current density of 4 A g⁻¹, outperforming the pristine MnO₂ sample.     

Centimeter-Sized Single Crystals of Dion-Jacobson Phase Lead-Free Double Perovskite for Efficient X-ray Detection

2D Dion–Jacobson (DJ) phase hybrid perovskites have shown great promise in the photoelectronic field owing to their outstanding optoelectronic performance and superior structural rigidity. However, DJ phase lead-free double perovskites are still a virgin land with direct X-ray detection. Herein, we have designed and synthesized a new DJ phase lead-free layered double perovskite of (HIS)₂AgSbBr₈ ( 1 , HIS²⁺ = histammonium). Centimeter-sized (18 × 10 × 5 mm³) single crystals of 1 are successfully grown via the temperature cooling technique, exhibiting remarkable semiconductive characteristics such as a high resistivity (2.2 × 10¹¹ Ω cm), a low trap state density (3.56 × 10¹⁰ cm⁻³), and a large mobility-lifetime product (1.72 × 10⁻³ cm² V⁻¹). Strikingly, its single-crystal-based X-ray detector shows a high sensitivity of 223 µC Gy⁻¹_air cm⁻² under 33.3 V mm⁻¹, a low detection limit (84.2 nGy_airs⁻¹) and superior anti-fatigue. As far as we know, we firstly demonstrates the potential of 2D DJ phase lead-free hybrid double perovskite in X-ray detection, showing excellent photoelectric response and operational stability. This work will pave a promising pathway to the innovative application of hybrid perovskites for eco-friendly and efficient X-ray detection.     

Novelty All-Inorganic Titanium-Based Halide Perovskite for Highly Efficient Photocatalytic CO2 Conversion

Lead halide perovskite materials have great potential for photocatalytic reaction due to their low fabrication cost, unique optical absorption coefficient, and suitable band structures. However, the main problems are the toxicity and instability of the lead halide perovskite materials. Therefore, a facile synthetic method is used to prepare lead-free environmentally friendly Cs₂TiX₆(X = Cl, Cl_0.5Br_0.5, Br) perovskite materials. Their structural and optical characteristics are systematically investigated. The band gaps of the produced samples are illustrated to be from 1.87 to 2.73 eV. Moreover, these materials can keep high stability in harsh environments such as illumination and heating, and the Cs₂Ti(Cl_0.5Br_0.5)₆ microcrystals demonstrate the yields of 176 µmol g⁻¹ for CO and 78.9 µmol g⁻¹ for CH₄ after light irradiation for 3 h, which is of the first report of Ti-based perovskite photocatalysts. This finding demonstrates that the Ti-based perovskites will create opportunities for photocatalytic applications, which may offer a new idea to construct low-cost, eco-friendly, and bio-friendly photocatalysts.     

Z-Scheme Modulated Charge Transfer on InVO4@ZnIn2S4 for Durable Overall Water Splitting

The charge transfer within heterojunction is crucial for the efficiency and stability of photocatalyst for overall water splitting (OWS). Herein, InVO₄ nanosheets have been employed as a support for the lateral epitaxial growth of ZnIn₂S₄ nanosheets to produce hierarchical InVO₄@ZnIn₂S₄ (InVZ) heterojunctions. The distinct branching heterostructure facilitates active site exposure and mass transfer, further boosting the participation of ZnIn₂S₄ and InVO₄ for proton reduction and water oxidation, respectively. The unique Z-scheme modulated charge transfer, visualized by simulation and in situ analysis, has been proved to promote the spatial separation of photoexcited charges and strengthen the anti-photocorrosion capability of InVZ. The optimized InVZ heterojunction presents improved OWS (153.3 µmol h⁻¹ g⁻¹ for H₂ and 76.9 µmol h⁻¹ g⁻¹ for O₂) and competitive H₂ production (21090 µmol h⁻¹ g⁻¹). Even after 20 times (100 h) of cycle experiment, it still holds more than 88% OWS activity and a complete structure.     

Robust Fabrication of Hybrid Lead-Free Perovskite Pellets for Stable X-ray Detectors with Low Detection Limit

X-ray detectors are widely utilized in medical diagnostics and nondestructive product inspection. Halide perovskites are recently demonstrated as excellent candidates for direct X-ray detection. However, it is still challenging to obtain high quality perovskites with millimeter-thick over a large area for high performance, stable X-ray detectors. Here, methylammonium bismuth iodide (MA₃Bi₂I₉) polycrystalline pellets (PPs) are developed by a robust, cost effective, and scalable cold isostatic-pressing for fabricating X-ray detectors with low limit of detection (LoD) and superior operational stability. The MA₃Bi₂I₉-PPs possess a high resistivity of 2.28 × 10¹¹ Ω cm and low dark carrier concentration of ≈10⁷ cm⁻³, and balanced mobility of ≈2 cm² V⁻¹ s⁻¹ for electrons and holes. These merits enable a sensitivity of 563 μC Gy_air⁻¹ cm⁻², a detection efficiency of 28.8%, and an LoD of 9.3 nGy_air s⁻¹ for MA₃Bi₂I₉-PPs detectors, and the LoD is much lower than the dose rate required for X-ray diagnostics used currently (5.5 μGy_air s⁻¹). In addition, the MA₃Bi₂I₉-PPs detectors work stably under high working bias field up to 2000 V cm⁻¹ after sensing an integrated dose >320 Gy_air with continuous X-ray radiation, demonstrating its competitive advantage in practical application. These findings provide an approach to explore a new generation of low LoD, stable and green X-ray detectors based on MA₃Bi₂I₉-PPs.     

Synthesis and crystal structures of a new (2,3-(CH3)2C6H3NH3)H2XO4 (X=P,As)

The aim of encapsulation of 2,3-dimethylanilinium cation in (H₂XO₄)_n polymeric anion chains is to build acentric frameworks that are efficient for non-linear optical (NLO) applications. The synthesis and structures of two new inorganic–organic NLO crystals with general formula (2,3-(CH₃)₂C₆H₃NH₃)H₂XO₄ (X=P, As) are reported. The magnitude of their second harmonic generations (SHG) responses was found to be between the KDP and urea. They crystallize with monoclinic unit-cells and are isotopic. We have determined the structure of phosphoric salt. The following unit-cell parameters were found: a=8.866(3) Å, b=5.909(6) Å, c=10.644(5) Å, β=112.44(1)°, V=515.5(5) Å³ and D_X=1.412 g cm⁻³. The space group is P2₁ with Z=2. The structure was refined with R=0.041 (R_w=0.057) for 1652 reflections with I≥3σ(I). It exhibits infinite (H₂PO₄)_nⁿ⁻ chains. The organic groups (2,3-(CH₃)₂C₆H₃NH₃)⁺ are anchored between adjacent polyanions through multiple hydrogen bonds. Chemical preparation, crystal structure, calorimetric and spectroscopic investigation are described.     

Metal-Free Hexagonal Perovskite High-Energetic Materials with NH3OH+/NH2NH3+ as B-Site Cations

Designing and synthesizing more advanced high-energetic materials for practical use via a simple synthetic route are two of the most important issues for the development of energetic materials. Through an elaborate design and rationally selected molecular components, two new metal-free hexagonal perovskite compounds, which are named as DAP-6 and DAP-7 with a general formula of (H₂dabco)B(ClO₄)₃ (H₂dabco²⁺ = 1,4-diazabicyclo[2.2.2]octane-1,4-diium), were fabricated via an easily scaled-up synthetic route using NH₃OH⁺ and NH₂NH₃⁺ as B-site cations, respectively. Compared with their NH₄⁺ analog ((H₂dabco)(NH₄)(ClO₄)₃; DAP-4), which has a cubic perovskite structure, DAP-6 and DAP-7 have higher crystal densities and enthalpies of formation, thus exhibiting higher calculated detonation performances. Specifically, DAP-7 has an ultrahigh thermal stability (decomposition temperatures (T_d) = 375.3 °C), a high detonation velocity (D = 8.883 km·s⁻¹), and a high detonation pressure (P = 35.8 GPa); therefore, it exhibits potential as a heat-resistant explosive. Similarly, DAP-6 has a high thermal stability (T_d = 245.9 °C) and excellent detonation performance (D = 9.123 km·s⁻¹, P = 38.1 GPa). Nevertheless, it also possesses a remarkably high detonation heat (Q = 6.35 kJ·g⁻¹) and specific impulse (I_sp = 265.3 s), which is superior to that of hexanitrohexaazaisowurtzitane (CL-20; Q = 6.23 kJ·g⁻¹, I_sp = 264.8 s). Thus, DAP-6 can serve as a promising high-performance energetic material for practical use.     

Preparation and characterization of some single,mixed and doped crystals and instrumentation aspects

The preparation and characterization (salient ones) of KAl (SO₄)₂. 12H₂O, KCr (SO₄)₂·12H₂O, mixed crystals of both with 10 to 90% of each component, mixed crystals of CsCl with CuCl₂, doped crystals of KBr with K₃FeCN₆, mixed crystals (NH₄)₂SO₄ with CuSO₄ or NiSO₄, NaCl with growth improver Pb⁺², Mn⁺², metallic crystals of Zn, Bi, ionic crystals of alkali halides with Pb⁺², or Cd⁺², etc. are presented. Instrumentation aspects of a rotary crystallizer, a homogeniser, an ingot release mechanism and a zone refiner are shown.     

Facile Proton Transport in Ammonium Borosulfate—An Unhumidified Solid Acid Polyelectrolyte for Intermediate Temperatures

High proton conductivity is reported for unhumidified ammonium borosulfate, NH₄[B(SO₄)₂], a solid acid coordination polymer that contains 1D, hydrogen-bonded NH₄⁺···¹_∞[B(SO₄)_4/2]⁻ chains. NH₄[B(SO₄)₂] is thermally stable to 320 °C and is amenable to sintering into monolithic, polycrystalline discs at 200 °C and about 300 MPa of uniaxial pressure. Impedance spectroscopy measurements reveal ionic conductivities for sintered ammonium borosulfate of 0.1 mS cm⁻¹ at 25 °C and up to 10 mS cm⁻¹ at 180 °C in ambient air. No superprotonic transition is observed in the temperature range of 25–180 °C. Ab initio molecular dynamics simulations show these high conductivities are aided by free rotation of the NH₄⁺ units and significant gyrational mobility of the SO₄ tetrahedra, which, in turn, provide facile pathways for proton locomotion. High conductivities, a wide operational temperature window, and tolerance to both ambient and anhydrous conditions make NH₄[B(SO₄)]₂ an attractive candidate electrolyte for intermediate-temperature hydrogen fuel cells that may enable operation at temperatures as high as 300 °C without active humidification.     

Ultralight,Heat-Insulated,and Tough PVA Hydrogel Hybridized with SiO2@cellulose Nanoclaws Aerogel via the Synergy of Hydrophilic and Hydrophobic Interfacial Interactions

Lightweight porous hydrogels provide a worldwide scope for functional soft mateirals. However, most porous hydrogels have weak mechanical strength, high density (>1 g cm⁻³), and high heat absorption due to weak interfacial interactions and high solvent fill rates, which severely limit their application in wearable soft-electronic devices. Herein, an effective hybrid hydrogel-aerogel strategy to assemble ultralight, heat-insulated, and tough polyvinyl alcohol (PVA)/SiO₂@cellulose nanoclaws (CNCWs) hydrogels (PSCG) via strong interfacial interactions with hydrogen bonding and hydrophobic interaction is demonstrated. The resultant PSCG has an interesting hierarchical porous structure from bubble template (≈100 µm), PVA hydrogels networks introduced by ice crystals (≈10 µm), and hybrid SiO₂ aerogels (<50 nm), respectively. PSCG shows unprecedented low density (0.27 g cm⁻³), high tensile strength (1.6 MPa) & compressive strength (1.5 MPa), excellent heat-insulated ability, and strain-sensitive conductivity. This lightweight porous and tough hydrogel with an ingenious design provides a new way for wearable soft-electronic devices.     

Constructing Co@TiO2 Nanoarray Heterostructure with Schottky Contact for Selective Electrocatalytic Nitrate Reduction to Ammonia

Electrochemical nitrate (NO₃⁻) reduction reaction (NO₃⁻RR) is a potential sustainable route for large-scale ambient ammonia (NH₃) synthesis and regulating the nitrogen cycle. However, as this reaction involves multi-electron transfer steps, it urgently needs efficient electrocatalysts on promoting NH₃ selectivity. Herein, a rational design of Co nanoparticles anchored on TiO₂ nanobelt array on titanium plate (Co@TiO₂/TP) is presented as a high-efficiency electrocatalyst for NO₃⁻RR. Density theory calculations demonstrate that the constructed Schottky heterostructures coupling metallic Co with semiconductor TiO₂ develop a built-in electric field, which can accelerate the rate determining step and facilitate NO₃⁻ adsorption, ensuring the selective conversion to NH₃. Expectantly, the Co@TiO₂/TP electrocatalyst attains an excellent Faradaic efficiency of 96.7% and a high NH₃ yield of 800.0 µmol h⁻¹ cm⁻² under neutral solution. More importantly, Co@TiO₂/TP heterostructure catalyst also presents a remarkable stability in 50-h electrolysis test.     

Microhardness studies in ammonium halide crystals

Microhardness studies of NH₄Cl (pure and doped), NH₄Br and alkali halide crystals are presented. The hardness of ammonium halides is found to be less as compared to alkali halide crystals. Doping NH₄Cl crystals with copper (Cu²⁺) is found to increase the hardness enormously and the results obtained with various concentrations of copper are presented. The results have been analysed and the various factors contributing to the increase in hardness at lower loads have been discussed.