Mechanochemical Synthesis of Aryl Fluorides by Using Ball Milling and a Piezoelectric Material as the Redox Catalyst

Aryl fluorides are important structural motifs in many pharmaceuticals. Although the Balz–Schiemann reaction provides an entry to aryl fluorides from aryldiazonium tetrafluoroborates, it suffers from drawbacks such as long reaction time, high temperature, toxic solvent, toxic gas release, and low functional group tolerance. Here, we describe a general method for the synthesis of aryl fluorides from aryldiazonium tetrafluoroborates using a piezoelectric material as redox catalyst under ball milling conditions in the presence of Selectfluor. This approach effectively addresses the aforementioned limitations. Furthermore, the piezoelectric material can be recycled multiple times. Mechanistic investigations indicate that this fluorination reaction may proceed via a radical pathway, and Selectfluor plays a dual role as both a source of fluorine and a terminal reductant.     

Geometry,groceries, and gardens: Learning mathematics and social justice through a nested,equity-directed instructional approach

We addressed the call for explorations of how BIPOC students’ “experiences in secondary mathematics classrooms might advance transformative, equity-focused, pedagogical models” (Joseph et al., 2019, p. 149) by exploring how a nested, equity-directed approach created different kinds of opportunities for students to take up, shift, or resist what it means to teach, learn, and do mathematics. Specifically, we looked at efforts to engage equity-directed dominant and critical approaches through a series of three mathematics projects aimed at investigating food insecurity as a social (in)justice issue using geometry. Our analysis focused on a subset of data generated during three projects from different times of the year. Findings revealed that the teacher more readily enacted critical equity-directed practices than dominant ones; that students more readily embraced those critical practices; and that students expected their use of mathematics and exploration of social issues to align with authentic, real-world situations.     

Synthesis of Fibrous Phosphorus Micropillar Arrays with Pyro-Phototronic Effects

The bottom-up preparation of two-dimensional material micro-nano structures at scale facilitates the realisation of integrated applications in optoelectronic devices. Fibrous Phosphorus (FP), an allotrope of black phosphorus (BP), is one of the most promising candidate materials in the field of optoelectronics with its unique crystal structure and properties.^[1] However, to date, there are no bottom-up micro-nano structure preparation methods for crystalline phosphorus allotropes.^{[1c, 2]} Herein, we present the bottom-up preparation of fibrous phosphorus micropillar (FP-MP) arrays via a low-pressure gas-phase transport (LP-CVT) method that controls the directional phase transition from amorphous red phosphorus (ARP) to FP. In addition, self-powered photodetectors (PD) of FP-MP arrays with pyro-phototronic effects achieved detection beyond the band gap limit. Our results provide a new approach for bottom-up preparation of other crystalline allotropes of phosphorus.     

Design of the Ionic Organic Nonlinear Optical Material NH4[LiC3H(CH3)O4] with Ultrawide Band Gap and Moderate Birefringence

Ionic organic crystals containing organic planar π-conjugated units has become one of the hot spots as nonlinear optical (NLO) materials. However, although this type of ionic organic NLO crystals commonly have remarkable second harmonic generation (SHG) responses, they also suffer from overlarge birefringences and relatively small band gaps that be hardly beyond 6.2 eV. Herein, a flexible π-conjugated [C₃H(CH₃)O₄]²⁻ unit was theoretically revealed, showing great potential for designing NLO crystals with balanced optical properties. Accordingly, through the reasonable NLO-favourable layered design, a new ionic organic material, NH₄[LiC₃H(CH₃)O₄], was successfully obtained. As expected, it achieves not only a large SHG effect (4×KDP), but also a suitable birefringence (0.06@546 nm) and an ultrawide band gap (>6.5 eV). This study provides a new flexible π-conjugated NLO-active unit, contributing to design more ionic organic NLO materials with excellent balanced optical properties.     

磷烯的研究进展与展望

黑磷晶体的单原子层结构被定义为磷烯，它具有独特的褶皱形态和一些区别于其它二维晶体材料的特性，如可调控的直接带隙，高开关比，高载流子迁移率以及优异的光学饱和吸收特性等，使其在纳米电子和纳米光学领域具有潜在应用价值.此外，蓝磷烯被理论计算所预测，它是黑磷烯的一种同素异形体，具有许多类似黑磷烯的优异特性.本文主要介绍了当前两种构型磷烯的研究进展，包括黑/蓝磷烯各自的晶体结构、制备方法、物理特性和稳定性；最后对目前磷烯研究中存在的问题与挑战提出了一些见解和展望.     

Cd/Pt Precursor Solution for Solar H2 Production and in situ Photochemical Synthesis of Pt Single-atom Decorated CdS Nanoparticles

Despite extensive efforts to develop high-performance H₂ evolution catalysts, this remains a major challenge. Here, we demonstrate the use of Cd/Pt precursor solutions for significant photocatalytic H₂ production (154.7 mmol g⁻¹ h⁻¹), removing the need for a pre-synthesized photocatalyst. In addition, we also report simultaneous in situ synthesis of Pt single-atoms anchored CdS nanoparticles (Pt_SA-CdS_IS) during photoirradiation. The highly dispersed in situ incorporation of extensive Pt single atoms on CdS_IS enables the enhancement of active sites and suppresses charge recombination, which results in exceptionally high solar-to-hydrogen conversion efficiency of ≈1 % and an apparent quantum yield of over 91 % (365 nm) for H₂ production. Our work not only provides a promising strategy for maximising H₂ production efficiency but also provides a green process for H₂ production and the synthesis of highly photoactive Pt_SA-CdS_IS nanoparticles.     

Birefringence Regulation by Clarifying the Relationship Between Stereochemically Active Lone Pairs and Optical Anisotropy in Tin-based Ternary Halides

It is important to establish and clarify the relationship between stereochemically active lone pairs and birefringence, since it is one of the significantly effective routes to explore birefringent crystals by introducing Sn-centered polyhedra with stereochemically active lone pairs. Herein, four tin(II)-based ternary halides A₃SnCl₅ and ASn₂Cl₅ (A=NH₄ and Rb) have been synthesized successfully. The experimental birefringence of Rb₃SnCl₅ and RbSn₂Cl₅ is larger than or equal to 0.046 and 0.123@546 nm, respectively. Through investigating the alkali or alkaline-earth metal tin(II)-based ternary halides, the structure-performance relationship has been concluded between stereochemically active lone pairs and optical anisotropy. It is beneficial to the analysis and prediction of birefringence in tin-based halides and provides a guide for exploring tin(II)-based optoelectronic functional materials.     

Quantum Phase Diagram of a Frustrated Spin-1/2 Ferro-Antiferromagnetic Normal Ladder

In this work, we consider a frustrated two-leg spin-1/2 ladder composed of Heisenberg ferromagnetic and antiferromagnetic spin-1/2 chains, and nearest spins from different legs interact via Heisenberg type rung exchange interactions that can be either ferromagnetic or antiferromagnetic in nature. The competing exchange interactions in the system lead to five different quantum phases like ferromagnetic, non-collinear ferrimagnetic (NCF), , antiferromagnetic and dimer phases. The  quantum phase diagram is constructed for the Heisenberg spin-1/2 model and the phases are characterized using the correlation functions which are calculated by the density matrix renormalization group method. We also analyze the  stability of phase and calculate the pitch angle in the NCF phase.     

Modelling of micro-electrochemical machining parameters used for machining of holes on copper plate

The electrochemical machining is a non-conventional machining process based on the electrolysis principle. It is used to machine various features on conducting engineering materials with the required accuracy and precision. So an attempt has been made to machine micro-holes on a 300 μm thick copper plate as an anode and a hollow stainless steel tool electrode of 250 μm diameter as the cathode. The machining operation is performed on the in-house developed micro-ECM experimental setup with controlled machining parameters voltage, concentration, and duty factor varied in three levels. A full factorial experimental plan is used to study the output responses material removal rate (MRR), radial overcut (ROC), circularity, and taper angle (TA). Later an adaptive neuro-fuzzy inference system (ANFIS) model has been developed and shown the effectiveness of the developed model in the paper. The Sugeno fuzzy model has been used in ANFIS to generate the fuzzy rules required for the model. Out of 27 experiments, 22 machining data are used for training the model, and the remaining 5 machining data are used for testing the developed model. The average error observed between the ANFIS predicted values and experimental values of MRR is 12.56%, circularity is 43.09%, ROC is 13%, and TA is 27.53%, respectively.     

Mechanisms of Biomolecular Self-Assembly Investigated Through In Situ Observations of Structures and Dynamics

Biomolecular self-assembly of hierarchical materials is a precise and adaptable bottom-up approach to synthesizing across scales with considerable energy, health, environment, sustainability, and information technology applications. To achieve desired functions in biomaterials, it is essential to directly observe assembly dynamics and structural evolutions that reflect the underlying energy landscape and the assembly mechanism. This review will summarize the current understanding of biomolecular assembly mechanisms based on in situ characterization and discuss the broader significance and achievements of newly gained insights. In addition, we will also introduce how emerging deep learning/machine learning-based approaches, multiparametric characterization, and high-throughput methods can boost the development of biomolecular self-assembly. The objective of this review is to accelerate the development of in situ characterization approaches for biomolecular self-assembly and to inspire the next generation of biomimetic materials.