Atomically Precise Mo2Cu17 Bimetallic Nanocluster: Synergistic Mo2O4-Coupled Copper Alkynyl Cluster for the Improved Hydrogen Evolution Reaction Performance.

Electrolytic hydrogen production via water splitting holds significant promise for the future of the energy revolution. The design of efficient and abundant catalysts, coupled with a comprehensive understanding of the hydrogen evolution reaction (HER) mechanism, is of paramount importance. In this study, we propose a strategy to craft an atomically precise cluster catalyst with superior HER performance by cocoupling a Mo2O4 structural unit and a Cu(I) alkynyl cluster into a structured framework. The resulting bimetallic cluster, Mo2Cu17, encapsulates a distinctive structure [Mo2O4Cu17(TC4A)4(PhC≡C)6], comprising a binuclear Mo2O4 subunit and a {Cu17(TC4A)2(PhC≡C)6} cluster, both shielded by thiacalix[4]arene (TC4A) and phenylacetylene (PhC≡CH). Expanding our exploration, we synthesized two homoleptic CuI alkynyl clusters coprotected by the TC4A and PhC≡C- ligands: Cu13 and Cu22. Remarkably, Mo2Cu17 demonstrates superior HER efficiency compared to its counterparts, achieving a current density of 10 mA cm-2 in alkaline solution with an overpotential as low as 120 mV, significantly outperforming Cu13 (178 mV) and Cu22 (214 mV) nanoclusters. DFT calculations illuminate the catalytic mechanism and indicate that the intrinsically higher activity of Mo2Cu17 may be attributed to the synergistic Mo2O4-Cu(I) coupling.

Casimir interaction with black phosphorus sheets.

We calculate the Casimir interaction between isotropic plates (gold or graphene) and black phosphorus (BP) sheets with Lifshitz theory. It is found that the Casimir force with BP sheets is of the order of α times the perfect metal limit, and α is the fine structure constant. Strong anisotropy of the BP conductivity gives rise to a difference in the Casimir force contribution between the two principal axis. Furthermore, increasing the doping concentration both in BP sheets and graphene sheets can enhance the Casimir force. Moreover, introducing substrate and increased temperature can also enhance the Casimir force, by this way we reveal that the Casimir interaction can be doubled. The controllable Casimir force opens a new avenue for designing next generation devices in micro- and nano-electromechanical systems.

A High-Precision Method of Stiffness Axes Identification for Axisymmetric Resonator Gyroscopes.

Axisymmetric resonators are key elements of Coriolis vibratory gyroscopes (CVGs). The performance of a CVG is closely related to the stiffness and damping symmetry of its resonator. The stiffness symmetry of a resonator can be effectively improved by electrostatic tuning or mechanical trimming, both of which need an accurate knowledge of the azimuth angles of the two stiffness axes of the resonator. Considering that the motion of a non-ideal axisymmetric resonator can be decomposed as two principal oscillations with two different natural frequencies along two orthogonal stiffness axes, this paper introduces a novel high-precision method of stiffness axes identification. The method is based on measurements of the phase difference between the signals detected at two orthogonal sensing electrodes when an axisymmetric resonator is released from all the control forces of the force-to-rebalance mode and from different initial pattern angles. Except for simplicity, our method works with the eight-electrodes configuration, in no need of additional electrodes or detectors. Furthermore, the method is insensitive to the variation of natural frequencies and operates properly in the cases of either large or small frequency splits. The introduced method is tested on a resonator gyroscope, and two stiffness axes azimuth angles are obtained with a resolution better than 0.1°. A comparison of the experimental results and theoretical model simulations confirmed the validity of our method.

A Novel Method for Estimating and Balancing the Second Harmonic Error of Cylindrical Fused Silica Resonators.

The cylindrical resonator gyroscope (CRG) is a type of Coriolis vibratory gyroscope which measures the angular velocity or angle through the precession of the elastic wave of the cylindrical resonator. The cylindrical fused silica resonator is an essential component of the CRG, the symmetry of which determines the bias drift and vibration stability of the gyroscope. The manufacturing errors breaking the symmetry of the resonator are usually described by Fourier series, and most studies are only focusing on analyzing and reducing the fourth harmonic error, the main error source of bias drift. The second harmonic error also is one of the obstacles for CRG towards high precision. Therefore, this paper provides a chemical method to evaluate and balance the second harmonic error of cylindrical fused silica resonators. The relation between the frequency split of the n = 1 mode and the second harmonic error of the resonator is obtained. Simulations are performed to analyze the effects of the first three harmonic errors on the frequency splits. The relation between the location of the low-frequency axis of n = 1 mode and the heavy axis of the second harmonic error is also analyzed by simulation. Chemical balancing experiments on two fused silica resonators demonstrate the feasibility of this balancing procedure, and show good consistency with theoretical and simulation analysis. The second harmonic error of the two resonators is reduced by 86.6% and 79.8%, respectively.

A 5.86 Million Quality Factor Cylindrical Resonator with Improved Structural Design Based on Thermoelastic Dissipation Analysis.

The cylindrical resonator is the core component of cylindrical resonator gyroscopes (CRGs). The quality factor (Q factor) of the resonator is one crucial parameter that determines the performance of the gyroscope. In this paper, the finite element method is used to theoretically investigate the influence of the thermoelastic dissipation (TED) of the cylindrical resonator. The improved structure of a fused silica cylindrical resonator is then demonstrated. Compared with the traditional structure, the thermoelastic Q (QTED) of the resonator is increased by 122%. In addition, the Q factor of the improved cylindrical resonator is measured, and results illustrate that, after annealing and chemical etching, the Q factor of the resonator is significantly higher than that of the cylindrical resonators reported previously. The Q factor of the cylindrical resonator in this paper reaches 5.86 million, which is the highest value for a cylindrical resonator to date.

Ultrafine antimony (Sb) nanoparticles encapsulated into a carbon microfiber framework as an excellent LIB anode with a superlong life of more than 5000 cycles.

Antimony (Sb) anode has attracted increasing attention given its high theoretical capacity and suitable working potential. Nonetheless, its practical application is largely hindered by huge volume changes during the cyclic process, resulting in unsatisfactory long-term cycled stabilities at high current density. In this work, large-scale ultrafine Sb nanoparticles are functionally designed to encapsulate into a 3D carbon microfiber framework (CMF) via a scalable electrospinning approach followed by a thermal treatment process. This fabrication strategy effectively avoids the change in the volume of the Sb anode and provides a fast conductive network to serve as an efficient 3D e/Li+ transport pathway. Benefiting from this novel structural design, an ultrafine Sb nanoparticles@carbon microfiber framework (U-Sb-NPs@CMF) composite anode used for lithium-ion batteries (LIBs) delivers a high reversible capacity of 622 mAh g-1 after 200 cycles at 0.5 A g-1 and 507 mAh g-1 after 2000 cycles at 2 Ag-1 and a high-capacity retention of 350 mAh g-1 even after 5000 long-term cycles. These outstanding charge-discharge performances suggest that the U-Sb-NPs@CMF composite is a promising candidate for an anode material in the application of LIBs.

Giant near-field radiative heat transfer between ultrathin metallic films.

Understanding energy transfer via near-field thermal radiation is essential for applications such as near-field imaging, thermophotovoltaics and thermal circuit devices. Evanescent waves and photon tunneling are responsible for the near-field energy transfer. In bulk noble metals, however, surface plasmons do not contribute efficiently to the near-field energy transfer because of the mismatch of wavelength. In this paper, a giant near-field radiative heat transfer rate that is orders-of-magnitude greater than the blackbody limit between two ultrathin metallic films is demonstrated at nanoscale separations. Moreover, different physical origins for near-field thermal radiation transfer for thick and thin metallic films are clarified, and the radiative heat transfer enhancement in ultrathin metallic films is proved to come from the excitation of surface plasmons. Meanwhile, because of the inevitable high sheet resistance of ultrathin metal films, the heat transfer coefficient is 4600 times greater than the Planckian limit for the separation of 10 nm in ultrathin metallic films, which is the same order or even greater than that in other 2D materials with low carrier density. Our work shows that ultrathin metallic films are excellent materials for radiative heat transfer, which may find promising applications in thermal nano-devices and thermal engineering.

Yellow Persistent Phosphor Ba13.35Al30.7Si5.3O70:Eu2+,Tm3+ from the Energy Regulation of Rare-Earth Ions.

The luminescence properties of Ba13.35Al30.7Si5.3O70:Eu2+ and Ba13.35Al30.7Si5.3O70:Eu2+,Tm3+ phosphors are presented. After being excited by a light source, Ba13.35Al30.7Si5.3O70:Eu2+,Tm3+ phosphors emit intense yellow long persistent luminescence covering the region from 450 to 700 nm, which can last about 8 h. Thermoluminescence curves were demonstrated to analyze the trapping nature of persistent luminescence. Tm3+ is added to improve the long persistent luminescence properties of phosphors. The mechanism of persistent luminescence has been studied.

Trimming of Imperfect Cylindrical Fused Silica Resonators by Chemical Etching.

The cylindrical resonator gyroscope (CRG) is a kind of solid-state gyroscope with a wide application market. The cylindrical resonator is the key component of CRG, whose quality factor and symmetry will directly affect the performance of the gyroscope. Due to the material properties and fabrication limitations, the actual resonator always has some defects. Therefore, frequency trimming, i.e., altering the local mass or stiffness distribution by certain methods, is needed to improve the overall symmetry of the resonator. In this paper, we made further derivation based on the chemical trimming theory proposed by Basarab et al. We built up the relation between the frequency split and the balanced mass to determine the mass to be removed. Chemical trimming experiments were conducted on three cylindrical fused silica resonators. The frequency splits of the three resonators were around 0.05 Hz after chemical trimming. The relation between frequency split and balanced mass established from experimental data was consistent with the theoretical calculation. Therefore, frequency split can be reduced to lower than 0.05 Hz under rigorous theoretical calculation and optimized chemical trimming parameters.

Optical and Electrical Method Characterizing the Dynamic Behavior of the Fused Silica Cylindrical Resonator.

Fused silica cylindrical resonant gyroscope (CRG) is a novel high-precision solid-wave gyroscope, whose performance is primarily determined by the cylindrical resonator's frequency split and quality factor (Q factor). The laser Doppler vibrometer (LDV) is extensively used to measure the dynamic behavior of fused silica cylindrical resonators. An electrical method was proposed to characterize the dynamic behavior of the cylindrical resonator to enhance the measurement efficiency and decrease the equipment cost. With the data acquisition system and the designed signal analysis program based on LabVIEW software, the dynamic behavior of the fused silica cylindrical resonator can be analyzed automatically and quickly. We compared all the electrical measurement results with the optical detection by LDV, demonstrating that the fast Fourier transform (FFT) result of the resonant frequency measured by the electrical method was 0.12 Hz higher than that with the optical method. Thus, the frequency split measured by the electrical and optical methods was the same in 0.18 Hz, and the measurement of the Q factor was basically the same in 730,000. We conducted all measurements under the same operation condition, and the optical method was used as a reference, demonstrating that the electrical method could characterize the dynamic behavior of the fused silica cylindrical resonator and enhance the measurement efficiency.

Cylindrical Fused Silica Resonators Driven by PZT Thin Film Electrodes with Q Factor Achieving 2.89 Million after Coating.

Cylindrical shell fused silica resonators coated with 8 axisymmetric Pb(Zr0.53Ti0.47)O3 (PZT) thin film electrodes (thickness ~2 µm) were reported. The resonators were firstly designed and fabricated, then annealed and processed by chemical etching to increase mechanical quality factor (Q factor) of resonators, which achieved as high as 2.89 million for n = 2 wineglass modes after being coated with PZT thin film electrodes. The n = 2 wineglass modes of the resonators were driven by PZT thin film electrodes in experiment and simulation with fine vibratory shape, which demonstrated the feasibility of the cylindrical fused silica resonator driven by PZT thin film electrodes. The application of PZT thin film electrodes to drive and detect cylindrical shell fused silica resonator can significantly improve Q factor of resonators and improve the sensitivity of Coriolis Vibratory Gyroscope (CVG).

Decreasing Frequency Splits of Hemispherical Resonators by Chemical Etching.

The hemispherical resonator gyroscope (HRG) has attracted the interest of the world inertial navigation community because of its exceptional performance, ultra-high reliability and its potential to be miniaturized. These devices achieve their best performance when the differences in the frequencies of the two degenerate working modes are eliminated. Mechanical treatment, laser ablation, ion-beams etching, etc., have all been applied for the frequency tuning of resonators, however, they either require costly equipment and procedures, or alter the quality factors of the resonators significantly. In this paper, we experimentally investigated for the first time the use of a chemical etching procedure to decrease the frequency splits of hemispherical resonators. We provide a theoretical analysis of the chemical etching procedure, as well as the relation between frequency splits and mass errors. Then we demonstrate that the frequency split could be decreased to below 0.05 Hz by the proposed chemical etching procedure. Results also showed that the chemical etching method caused no damage to the quality factors. Compared with other tuning methods, the chemical etching method is convenient to implement, requiring less time and labor input. It can be regarded as an effective trimming method for obtaining medium accuracy hemispherical resonator gyroscopes.

Material and Ingenious Synthesis Strategy for Short-Wavelength Infrared Light-Emitting Device.

Infrared (IR) light-emitting materials have wide applications. However, variety and economical accesses to obtain IR materials and devices are still limited, because the IR-emitting materials are always suffering from two obstacles, namely, lower absorption and lower emission efficiency. In this work, using a modified high-temperature solid-state reaction an efficient short-wavelength IR luminescent material is successfully synthesized. On the basis of the excellent luminescent properties, a convenient IR light-emitting diode (LED) device is fabricated by combining the novel IR material with a commercial UV LED chip. Besides the anticipation that it may lead to a boost of the application of IR device in different fields, importantly, we also consider that the ingenious synthesis strategy may open a door for obtaining novel ions doped functional materials.

A novel dichromic self-referencing optical probe SrO:Bi(3+),Eu(3+) for temperature spatially and temporally imaging.

A novel dichromic luminescence probe SrO:Eu(3+),Bi(3+) for temperature sensing is achieved. The detailed luminescence properties, e.g., the excitation emission spectra, energy transfer efficiency, luminescence decay lifetimes and temperature dependent luminescence are comprehensively studied. The two dominant emissions (5)D0→(7)F2 transition of Eu(3+) and the (3)P1→(1)S0 transition of Bi(3+) display adjustable spectrum area. The interaction effect between Eu(3+) and Bi(3+) are proposed. The dichromic emissions are specifically responding to temperature with high sensitivity at ultra-wide range from 30 to 400 °C. Spatial and temporal temperature images on an aircraft surface have been successfully realized under excitation of commercial 365 nm light emitting diode (LED) by painting the SrO:Bi(3+),Eu(3+) phosphor on a plane model. Finally, the thermal quenching mechanism revealed by Arrhenius theory is employed to interpret the temperature sensitive luminescence behaviour.

Sr9Mg(1.5)(PO4)7:Eu(2+): A Novel Broadband Orange-Yellow-Emitting Phosphor for Blue Light-Excited Warm White LEDs.

A new orange-yellow-emitting Sr9Mg(1.5)(PO4)7:Eu(2+) phosphor was prepared via high-temperature solid-state reaction. The structure and optical properties of it were studied systematically. Sr9Mg(1.5)(PO4)7:Eu(2+) can be well-excited by 460 nm blue InGaN chips and exhibit a wide emission band covering from 470 to 850 nm with two main peaks centered at 523 and 620 nm, respectively, which originate from 5d-4f dipole-allowed transitions of Eu(2+) in different crystallographic sites. The sites attribution, concentration quenching, fluorescence decay analysis, and temperature-dependent luminescence properties were investigated in detail. Furthermore, a warm white LED device was fabricated by combining a 460 nm blue InGaN chip with the optimized orange-yellow-emitting Sr9Mg(1.5)(PO4)7:Eu(2+). The color coordinate, correlated color temperature and color rendering index of the fabricated LED device were (0.393, 0.352), 3437 K, and 86.07, respectively. Sr9Mg(1.5)(PO4)7:Eu(2+) has great potential to serve as an attractive candidate in the application of blue light-excited warm white LEDs.

Reduction of Eu(3+) due to a change of the topological structure of the BO3 unit in borate glass.

Adjusting and controlling an ion's chemical state has always been a focus of researchers' attention. Herein, an intense long-lasting phosphorescence of Eu(2+) is obtained without any sacrificial reductant. The remarkable self-reducing process and the unique luminescence properties stem from a variation of the topological structure of the BO3 triangle.

Tri-chromatic white-light emission from a single-phase Ca9Sc(PO4)7:Eu(2+),Tb(3+),Mn(2+) phosphor for LED applications.

A series of single-phase Ca9Sc(PO4)7:Eu(2+),Tb(3+),Mn(2+) phosphors for UV excitations were synthesized by a high-temperature solid-state reaction. Energy transfer from Eu(2+)→ Tb(3+) and Eu(2+)→ Mn(2+) in a Ca9Sc(PO4)7 sample is a feasible route to realize color-tunable emission because Ca9Sc(PO4)7 single-doped Eu(2+)/Tb(3+)/Mn(2+) emit blue, green and red light, respectively. Most of the white light region in the CIE chromaticity diagram has been realized in Ca9Sc(PO4)7:Eu(2+),Tb(3+),Mn(2+) phosphors. Warm white light including the points of (0.337, 0.331), (0.353, 0.355) and (0.358, 0.327) close to day light (0.33, 0.33) with CCT of 5285 K, 4719 K and 4333 K is obtained, respectively.

Investigation on Luminescence Properties of a Long Afterglow Phosphor Ca2SnO4:Tm³âº.

A series of new long afterglow phosphors Ca2 SnO4:xTm(3+) were synthesized by using traditional solid-state reactions. XRD measurements and Rietveld refinement revealed that the incorporation of the Tm(3+) dopants generated no second phase other than the original one of Ca2 SnO4, which indicated that the dopants completely merged into the host. The corresponding optical properties were further systematically studied by photoluminescence, phosphorescence, and thermoluminescence (TL) spectroscopy. The results show that the Tm(3+)-related defects account for the bright bluish green afterglow emission from the characteristic f-f transitions of Tm(3+) ions. The bluish green long-lasting phosphorescence could be observed for 5 h by the naked eye in a dark environment after the end of UV irradiation. Two TL peaks at 325 and 349 K from the TL curves were adopted to calculate the depth of the traps, which were 0.45 and 0.78 eV, respectively. The mechanism of the long afterglow emission was also explored.

Single-phased white-light-emitting Ca4(PO4)2O:Ce³âº,Eu²âº phosphors based on energy transfer.

A novel single-composition Ca4(PO4)2O:Ce(3+),Eu(2+) phosphor emitting white light was synthesized by conventional solid-state reaction for light-emitting diode applications. X-ray diffraction, photoluminescence spectra, and luminescence decay spectra were used to characterize the samples. Energy transfer from Ce(3+) to Eu(2+) ions was observed in the co-doped samples, and the transfer mechanism in the Ca4(PO4)2O:Ce(3+),Eu(2+) phosphors was dipole-dipole interaction. The emission hue of Ca4(PO4)2O:Ce(3+),Eu(2+) was found to vary from blue (0.165, 0.188) to white (0.332, 0.300) and eventually to orange (0.519, 0.366) by precisely controlling the ratio of Ce(3+) to Eu(2+). The combination of a 380 nm near-ultraviolet chip with a Ca4(PO4)2O:0.02Ce(3+),0.012Eu(2+) phosphor produced a diode emitting white light with ultra-wideband emission and a correlated color temperature of 4124 K. Overall, results indicated that the prepared samples may be potentially applied in white-light-emitting diodes.

Tunable long lasting phosphorescence due to the selective energy transfer from defects to luminescent centres via tunnelling in Mn(2+) and Tm(3+) co-doped zinc pyrophosphate.

A series of new phosphors Zn2(0.97-x)P2O7:0.06Tm(3+),2xMn(2+) (0 ≤ x ≤ 0.05) were synthesized and their luminescence properties were investigated. The results showed that the defects in all the phosphors were related to Tm(3+), and Mn(2+) merely served as the emission centres. Tm(3+) also acted as an emission centre and yielded blue phosphorescence corresponding to its characteristic f-f emissions in the phosphors where the Mn(2+) concentration was low (x ≤ 0.001), while in the phosphors with high concentrations of Mn(2+) it mainly served as a defect by forming Tm. The electrons thermally released from defects selectively transferred to Mn(2+) centres mainly through thermally-assisted tunnelling and this resulted in their red to near-infrared phosphorescence. By adjusting the ratio of Mn(2+) to Tm(3+) to control the spectral distribution, tunable long lasting phosphorescence from blue to near-infrared was achieved.