Two-Dimensional MOF Constructed by a Binuclear-Copper Motif for High-Performance Electrocatalytic NO Reduction to NH3.

Ambient electrochemical NO reduction presents a dual solution for sustainable NO reduction and NH3 synthesis. However, their complex kinetics and energy demands necessitate high-performance electrocatalysts to ensure effective and selective process outcomes. Herein, we report that a two-dimensional Cu-based metal-organic framework (MOF), {[Cu(HL)]·H2O} n , (Cu-OUC, H3L = 5-(2'-carboxylphenoxy)isophthalic acid) acts as a stable electrocatalyst with high efficiency for NO-to-NH3 conversion. Electrochemical experimental studies showed that in 0.1 M K2SO4 solution, the as-prepared Cu-OUC achieved a peak Faradaic efficiency of 96.91% and a notable NH3 yield as high as 3415.82 µg h-1 mg-1. The Zn-NO battery in aqueous solution can produce electricity possessing a power density of 2.04 mW cm-2 while simultaneously achieving an NH3 yield of 616.92 µg h-1 mg-1. Theoretical calculations revealed that the surface of Cu-OUC effectively facilitates NO activation through a two-way charge transfer mechanism of "electron acceptance and donation", with the *NO formation step being the potential-determining stage. The study pioneers the use of a MOF as an electrocatalyst for ambient NO-to-NH3 conversion.

Enhancing Effect of Fullerene Guest and Counterion on the Structural Stability and Electrical Conductivity of Octahedral Metallo-Supramolecular Cages.

Metallo-supramolecular cages have garnered tremendous attention for their diverse yet molecular-level precision structures. However, the physical properties of these supramolecular ensembles, which are of potential significance in molecular electronics, remain largely unexplored. We herein constructed a series of octahedral metallo-cages and cage-fullerene complexes with notably enhanced structural stability. As such, we could systematically evaluate the electrical conductivity of these ensembles at both the single-molecule level and aggregated bulk state (as well-defined films). Our findings reveal that counteranions and fullerene guests play a pivotal role in determining the electrical conductivity of the aggregated state, while such effects are less significant for single-molecule conductance. Both the counteranions and fullerenes effectively tune the electronic structures and packing density of metallo-supramolecular assemblies, and facilitate efficient charge transfer between the cage hosts and fullerenes, resulting in a notable one order of magnitude increase in the electrical conductivity of the aggregated state.

Enantiomerically Resolvable Inherent Chirality Induced by Strong Para-Steric Hindrance in Cycloparaphenylene-Based Carbon Nanohoops.

The chemical modification of the achiral carbon nanohoops to break the symmetry will result in inherently chiral structures with interesting optical properties. Herein, we report two novel π-extended chiral macrocycles, cyclo[10]paraphenylene-pyrene ([10]CPP-2Pyrene) and cyclo[10]paraphenylene-hexa-peri-hexabenzocoronene ([10]CPP-2HBC). The large substituents on the nanohoop peripheries effectively prevented free rotation and the racemization process. The conformation of each enantiomer is stable enough to be resolved by recycling HPLC.

Ln3+ Induced Thermally Activated Delayed Fluorescence of Chiral Heterometallic Clusters Ln2Ag28.

A series of TADF-active compounds: 0D chiral Ln-Ag(I) clusters L-/D-Ln2Ag28-0D (Ln=Eu/Gd) and 2D chiral Ln-Ag(I) cluster-based frameworks L-/D-Ln2Ag28-2D (Ln=Gd) has been synthesized. Atomic-level structural analysis showed that the chiral Ag(I) cluster units {Ag14S12} in L-/D-Ln2Ag28-0D and L-/D-Ln2Ag28-2D exhibited similar configurations, linked by varying numbers of [Ln(H2O)x]3+ (x=6 for 0D, x=3 for 2D) to form the final target compounds. Temperature-dependent emission spectra and decay lifetimes measurement demonstrated the presence of TADF in L-Ln2Ag28-0D (Ln=Eu/Gd) and L-Gd2Ag28-2D. Experimentally, the remarkable TADF properties primarily originated from {Ag14S12} moieties in these compounds. Notably, {Ag14S12} in L-Eu2Ag28-0D and L-Gd2Ag28-2D displayed higher promote fluorescence rate and shorter TADF decay times than L-Gd2Ag28-0D. Combined with theoretical calculations, it was determined that the TADF behaviors of {Ag14S12} cluster units were induced by 4 f perturbation of Ln3+ ions. Specially, while maintaining ΔE(S1-T1) small enough, it can significantly increase k(S1→S0) and reduce TADF decay time by adjusting the type or number of Ln3+ ions, thus achieving the purpose of improving TADF for cluster-based luminescent materials.

Metal-support spin orders: Crucial effect on electrocatalytic oxygen reduction.

Magnetic property (e.g. spin order) of support is of great importance in the rational design of heterogeneous catalysts. Herein, we have taken the Ni-supported ferromagnetic (FM) CrBr3 support (Nix/CrBr3) to thoroughly investigate the effect of spin-order on electrocatalytic oxygen reduction reaction (ORR) via spin-polarized density functional theory calculations. Specifically, Ni loading induces anti-FM coupling in Ni-Cr, leading to a transition from FM-to-ferrimagnetic (FIM) properties, while Ni-Ni metallic bonds create a robust FM direct exchange, benefiting the improvement of the phase transition temperature. Interestingly, with the increase in Ni loading, the easy magnetic axis changes from out-of-plane (2D-Heisenberg) to in-plane (2D-XY). The adsorption properties of Nix/CrBr3, involving O2 adsorption energy and configuration, are not governed by the d-band center but strongly correlate with magnetic anisotropy. It is noteworthy that the applied potential and electrolyte acidity triggers spin-order transition phenomena during the ORR and induces the catalytic pathway change from 4e- ORR to 2e- ORR with the excellent onset potential of 0.93 V/reversible hydrogen electrode, comparable to the existing most excellent noble-metal catalysts. Generally, these findings offer new avenues to understand and design heterogeneous catalysts with magnetic support.

Accurate Prediction of the Magnetic Ordering Temperature of Ultralow-Temperature Magnetic Refrigerants.

Adiabatic demagnetization refrigeration is known to be the only cryogenic refrigeration technology that can achieve ultralow temperatures (≪1 K) at gravity-free conditions. The key indexes to evaluate the performance of magnetic refrigerants are their magnetic entropy changes (-ΔSm) and magnetic ordering temperature (T0). Although, based on the factors affecting the -ΔSm of magnetic refrigerants, one has been able to judge if a magnetic refrigerant has a large -ΔSm, how to accurately predict their T0 remains a huge challenge due to the fact that the T0 of magnetic refrigerants is related to not only magnetic exchange but also single-ion anisotropy and magnetic dipole interaction. Here, we, taking GdCO3F (1), Gd(HCOO)F2, Gd2(SO4)3·8H2O, GdF3, Gd(HCOO)3 and Gd(OH)3 as examples, demonstrate that the T0 of magnetic refrigerants with very weak magnetic interactions and small anisotropy can be accurately predicted by integrating mean-field approximation with quantum Monte Carlo simulations, providing an effective method for predicting the T0 of ultralow-temperature magnetic refrigerants. Thus, the present work lays a solid foundation for the rational design and preparation of ultralow-temperature magnetic refrigerants in the future.

Magnetic Order Transition of a Two-Dimensional Square-Lattice Electrocatalyst Assembled by Fe-N4 Units: Crucial Role on Oxygen Reduction.

Herein, we theoretically investigate the effect of magnetic orders on electrocatalytic oxygen reduction reaction (ORR) properties on the Fe-N4 site-embedded two-dimensional (2D) covalent organic framework (Fe-N4@COF-C3N2) under realistic environments. The Fe-N4@COF-C3N2 shows a 2D square-lattice (sql) topology with three magnetic order states: one ferromagnetic state (FM) and two antiferromagnetic states (AFM1 and AFM2). Specially, the electrocatalyst in the AFM2 state shows a remarkable onset potential of 0.80 V/reversible hydrogen electrode (RHE) at pH 1, superior to the existing most excellent noble-metal catalysts. Thermodynamically, the onset potential for the 4e- ORR is 0.64 V/RHE at pH 1, with a magnetic state transition process of FM → AFM1 → FM → FM → FM, while at pH 13, the onset potential for the 4e- ORR is 0.54 V/RHE, with the magnetic transition process of FM → FM → AFM1 → FM → FM. Generally, this finding will provide new avenues to rationally design the Fe-N4 electrocatalyst.

A Strained Donor-Acceptor Carbon Nanohoop: Synthesis, Photophysical and Charge Transport Properties.

Herein, we report the synthesis of a novel intramolecular donor-acceptor (D-A) system ([12]CPP-8TPAOMe) based on cycloparaphenylenes (CPPs) grafted with eight di(4-methoxyphenyl)amino groups (TPAOMe) as donors. Compared to [12]CPP, D-A nanohoop exhibited significant changes in physical properties, including a large redshift (>78 nm) in the fluorescence spectrum and novel positive solvatofluorochromic properties with a maximum peak ranging from 484 nm to 546 nm. The potential applications of [12]CPP-8TPAOMe in electron- and hole-transport devices were further investigated, and its bipolar behavior as a charge transport active layer was clearly observed.

Anomalous anti-Kasha excited-state luminescence from symmetry-breaking heterogeneous carbon bisnanohoops.

It is a long-standing scientific controversy to achieve anti-Kasha-type multiple emissions by tuning the structures at a molecular level. Although it is known that some conjugated structures have excitation-dependent multiple emissions, no all-benzenoid molecules have yet been reported, the emissions of which originate from different excited states. Herein, we report the design of two symmetry-breaking heterogeneous carbon bisnanohoops that in solution become multiple fluorescent emitters with unusual anti-Kasha characteristics. This phenomenon can be spectroscopically and theoretically explained and will find applications in a wide range of sensing and imaging technologies.

Tuning Electrocatalytic Water Oxidation Activity: Insights from the Active-Site Distance in LnCu6 Clusters.

Atomically precise metal clusters serve as a unique model for unraveling the intricate mechanism of the catalytic reaction and exploring the complex relationship between structure and activity. Herein, three series of water-soluble heterometallic clusters LnCu6, abbreviated as LnCu6-AC (Ln = La, Nd, Gd, Er, Yb; HAC = acetic acid), LnCu6-IM (Ln = La and Nd; IM = Imidazole), and LnCu6-IDA (Ln = Nd; H2IDA = Iminodiacetic acid) are presented, each featuring a uniform metallic core stabilized by distinct protected ligands. Crystal structure analysis reveals a triangular prism topology formed by six Cu2+ ions around one Ln3+ ion in LnCu6, with variations in Cu···Cu distances attributed to different ligands. Electrocatalytic oxygen evolution reaction (OER) shows that these different LnCu6 clusters exhibit different OER activities with remarkable turnover frequency of 135 s-1 for NdCu6-AC, 79 s-1 for NdCu6-IM and 32 s-1 for NdCu6-IDA. Structural analysis and Density Functional Theory (DFT) calculations underscore the correlation between shorter Cu···Cu distances and improves OER catalytic activity, emphasizing the pivotal role of active-site distance in regulating electrocatalytic OER activities. These results provide valuable insights into the OER mechanism and contribute to the design of efficient homogeneous OER electrocatalysts.

Axially Coordinated Gold Nanoclusters Tailoring Fe-N-C Nanozymes for Enhanced Oxidase-Like Specificity and Activity.

Metal-organic frameworks (MOF) derived nitrogen-doped carbon-supported monodisperse Fe (Fe-N-C) catalysts are intensively studied, but great challenges remain in understanding the relationship between the coordination structure and the performance of Fe-N-C nanozymes. Herein, a novel nanocluster ligand-bridging strategy is proposed for constructing Fe-S1 N4 structures with axially coordinated S and Au nanoclusters on ZIF-8 derived Fe-N-C (labeled Aux /Fe-S1 N4 -C). The axial Au nanoclusters facilitate electron transfer to Fe active sites, utilizing the bridging ligand S as a medium, thereby enhancing the oxygen adsorption capacity of composite nanozymes. Compared to Fe-N-C, Aux /Fe-S1 N4 -C exhibits high oxidase-like specificity and activity, and holds great potential for detecting acetylcholinesterase activity with a detection limit of 5.1 µU mL-1 , surpassing most reported nanozymes.

Visible-Light Photocatalytic Overall Water Splitting on a B4C3/CxNy Z-Scheme Heterojunction: Role of Ultrafast Carrier Recombination-Transfer Kinetics.

Herein, combining density functional theory (DFT) calculations with nonadiabatic molecular dynamics (NAMD), we built a computational framework to rationally screen from a series of 2D conjugated carbon nitrides (CNs) to match with B4C3, resulting in the excellent direct Z-scheme photocatalyst (B4C3/C6N6) for overall water splitting (OWS). Studies on interface engineering and ultrafast dynamics of carrier recombination-transfer show that in the B4C3/C6N6 system, compared with the slower interlayer migration process of carriers, strong nonadiabatic coupling and longer quantum decoherence time accelerates weak carrier interlayer recombination on a subpicosecond time scale, enabling simultaneous triggering of hydrogen evolution reaction (HER) with ΔG = -0.23 eV and spontaneous oxygen evolution reaction (OER) in the absence of sacrificial or cocatalysts. In general, our work will promote the design of efficient direct Z-scheme photocatalysts from an ultrafast dynamics perspective.

A metal-free photoactive nitrogen-doped carbon nanosolenoid with broad absorption in visible region for efficient photocatalysis.

Riemann surfaces inspired chemists to design and synthesize such multidimensional curved carbon architectures. It has been predicted that carbon nanosolenoid materials with Riemann surfaces have unique structures and novel physical properties. Here we report the first synthesis of a nitrogen-doped carbon nanosolenoid (N-CNS) using bottom-up approach with a well-defined structure. N-CNS was obtained by a rational Suzuki polymerization, followed by oxidative cyclodehydrogenation. The successful synthesis of N-CNS was fully characterized by GPC, FTIR, solid-state 13C NMR and Raman techniques. The intrinsic single-strand molecular structures of N-CNS helices can be clearly resolved using low-dose integrated differential phase contrast scanning transmission electron microscopy (iDPC-STEM) technique. Possessing unique structural and physical properties, this long π-extended polymer N-CNS can provide new insight towards bottom-up syntheses of curved nanoribbons and potential applications as a metal-free photocatalyst for visible-light-driven H2 evolution and highly efficient photocatalyst for photoredox organic transformations.

Plastic side flow and elastic recovery influences on optical diffraction effect of diamond turning: theoretical simulation and experimental verification.

Spherical/aspherical mirrors are widely used in optical systems and imaging systems, but their reflectivity is affected by the surface roughness. In this study, the effects of plastic side flow and elastic recovery on the diffraction phenomenon and reflectivity are analyzed systematically. The energy ratio of an ultra-precision turning surface is calculated by rigorous coupled-wave method, the influence of aberration on diffraction efficiency is considered in combination with the specific structural parameters of spherical/aspherical surface, and the appropriate measuring beam diameter is selected. Through predicted results and experimental observations, it can be found that with the increase of plastic side flow height, the energy ratio of zero-order diffracted light reduces, the brightness weakens, and the diffraction light spots become more obvious. This is because large plastic side flow height leads to more complex three-dimensional surface topography and great roughness P-V value. The influence of elastic recovery on the reflectivity is different from that of plastic side flow. As the elastic recovery increases, the roughness P-V value lessens. As a result, the energy ratio of zero-order diffracted light enlarges, and the brightness strengthens. This paper provides a theoretical basis for machining of spherical/aspheric mirrors with high reflectivity.

Influence of cutting parameters on system vibration and optical performance of diamond turned optics.

In this paper the influence of vibration on reflectivity is systematically analyzed. A three-dimensional topography model of a machined surface considering vibration is established first. Based on the three-dimensional morphology model, the reflectivity of a diamond turned surface is calculated by a rigorous coupled wave method. The influences of cutting parameters on the diffraction effect of a diamond turned surface are discussed. The predicted and experimental results reveal that as the vibration intensifies with an increase in cutting depth and feed rate, the peak-valley (PV) roughness of the machined surface increases, which yields an increasing diffraction effect, i.e., resulting in a decrease in reflectivity. When the spindle speed is low, the tool and workpiece have a small sliding velocity, causing a great deal of friction, which amplifies the deformation of the workpiece surface. In this case, the PV value of the machined surface roughness is large, leading to a greater diffraction effect and bad reflectivity. With the increment of spindle rotation speed, the friction is relieved quickly, but the vibration is intensified, which produces increasing reflectivity. When the spindle speed is set to about 1200r/min, the reflectivity reaches the maximum value. When the spindle speed is larger than 1200r/min, the increase of vibration is dominant, resulting in a gradual increase in PV surface roughness and a decrease in reflectivity.

Conductive Lanthanide Metal-Organic Frameworks with Exceptionally High Stability.

Electrically conductive metal-organic frameworks (MOFs) have been extensively studied for their potential uses in energy-related technologies and sensors. However, achieving that goal requires MOFs to be highly stable and maintain their conductivity under practical operating conditions with varying solution environments and temperatures. Herein, we have designed and synthesized a new series of {[Ln4(µ4-O)(µ3-OH)3(INA)3(GA)3](CF3SO3)(H2O)6}n (denoted as Ln4-MOFs, Ln = Gd, Tm, and Lu, INA = isonicotinic acid, GA = glycolic acid) single crystals, where electrons are found to transport along the π-π stacked aromatic carbon rings in the crystals. The Ln4-MOFs show remarkable stability, with minimal changes in conductivity under varying solution pH (1-12), temperature (373 K), and electric field as high as 800 000 V/m. This stability is achieved through the formation of strong coordination bonds between high-valent Ln(III) ions and rigid carboxylic linkers as well as hydrogen bonds that enhance the robustness of the electron transport path. The demonstrated lanthanide MOFs pave the way for the design of stable and conductive MOFs.

Recent advances in developing multiscale descriptor approach for the design of oxygen redox electrocatalysts.

Oxygen redox electrocatalysis is the crucial electrode reaction among new-era energy sources. The prerequisite to rationally design an ideal electrocatalyst is accurately identifying the structure-activity relationship based on the so-called descriptors which link the catalytic performance with structural properties. However, the quick discovery of those descriptors remains challenging. In recent, the high-throughput computing and machine learning methods were identified to present great prospects for accelerating the screening of descriptors. That new research paradigm improves cognition in the way of oxygen evolution reaction/oxygen reduction reaction activity descriptor and reinforces the understanding of intrinsic physical and chemical features in the electrocatalytic process from a multiscale perspective. This review summarizes those new research paradigms for screening multiscale descriptors, especially from atomic scale to cluster mesoscale and bulk macroscale. The development of descriptors from traditional intermediate to eigen feature parameters has been addressed which provides guidance for the intelligent design of new energy materials.

Regulating supramolecular interactions in dimeric macrocycles.

Supramolecular behavior is highly dependent on many factors, including complicated microenvironments and weak interactions. Herein, we describe tuning supramolecular architectures of rigid macrocycles by synergistic effects of their geometric configurations, sizes, and guests. Two paraphenylene-based macrocycles are anchored onto different positions in a triphenylene derivative, resulting in dimeric macrocycles with different shapes and configurations. Interestingly, these dimeric macrocycles show tunable supramolecular interactions with guests. In solid state, a 2 : 1 host-guest complex was observed between 1a and C60/C70, while an unusual 2 : 3 host-guest complex 3C60@(1b)2 can be observed between 1b and C60. This work expands the scope of the synthesis of novel rigid bismacrocycles and provides a new strategy to construct different supramolecular systems.

Research on the Method of Reducing Dynamic Cutting Force in Aspheric Machining.

With the rapid development of photoelectric communication and other fields, the demand for high-precision aspheric mirrors has been increasing. Predicting dynamic cutting forces is vital in selecting machining parameters and also affects the surface quality of the machined surface. This study comprehensively considers the effects of different cutting parameters and workpiece shape parameters on dynamic cutting force. The actual width of cut, depth of cut, and shear angle are modelled while considering the effects of vibration. A dynamic cutting-force model considering the aforementioned factors is then established. Using experimental results, the model accurately predicts the average value of dynamic cutting force under different parameters and the range of fluctuation of dynamic cutting force, with a controlled relative error of about 15%. The influence of workpiece shape and workpiece radial size on dynamic cutting force is also considered. The experimental results show that the greater the surface slope, the more dramatic the dynamic cutting force fluctuations. This lays the foundation for subsequent writing on vibration suppression interpolation algorithms. The influence of the radius of the tool tip on dynamic cutting forces leads to the conclusion that to achieve the goal of reducing the fluctuation of cutting forces, diamond tools with different parameters should be selected for different feed rates. Finally, a new interpolation-point planning algorithm is used to optimize the position of interpolation points in the machining process. This proves the reliability and practicability of the optimization algorithm. The results of this study are of great significance to the processing of high-reflectivity spherical/aspheric surfaces.

Magnetoelectric effect generated through electron transfer from organic radical to metal ion.

Magnetoelectric (ME) materials induced by electron transfer are extremely rare. Electron transfer in these materials invariably occurs between the metal ions. In contrast, ME properties induced by electron transfer from an organic radical to a metal ion have never been observed. Here, we report the ME coupling effect in a mononuclear molecule-based compound [(CH3)3NCH2CH2Br][Fe(Cl2An)2(H2O)2] (1) [Cl2An = chloranilate, (CH3)3NCH2CH2Br+ = (2-bromoethyl)trimethylammonium]. Investigation of the mechanism revealed that the ME coupling effect is realized through electron transfer from the Cl2An to the Fe ion. Measurement of the magnetodielectric (MD) coefficient of 1 indicated a positive MD of up to ∼12% at 103.0 Hz and 370 K, which is very different from that of ME materials with conventional electron transfer for which the MD is generally negative. Thus, the current work not only presents a novel ME coupling mechanism, but also opens a new route to the synthesis of ME coupling materials.