In situ Raman spectroscopic study towards the growth and excellent HER catalysis of Ni/Ni(OH)2 heterostructure

The electrochemical water splitting to produce H₂ in high efficiency with earth-abundant-metal catalysts remains a challenge. Here, we describe a simple “cyclic voltammetry + ageing” protocol at room temperature to activate Ni electrode (AC-Ni/NF) for hydrogen evolution reaction (HER), by which Ni/Ni(OH)₂ heterostructure is formed at the surface. In situ Raman spectroscopy reveals the gradual growth of Ni/Ni(OH)₂ heterostructure during the first 30 min of the aging treatment and combined with polarization measurements, it suggests a positive relation between the Ni/Ni(OH)₂ amount and HER performance of the electrode. The obtained AC-Ni/NF catalyst, with plentiful Ni–Ni(OH)₂ interfaces, exhibits remarkable performance towards HER, with the low overpotential of only 30 mV at a H₂-evolving current density of 10 mA/cm² and 153 mV at 100 mA/cm², as well as a small Tafel slope of 46.8 mV/dec in 1 M KOH electrolyte at ambient temperature. The excellent HER performance of the AC-Ni/NF could be maintained for at least 24 h without obvious decay. Ex situ experiments and in situ electrochemical-Raman spectroscopy along with density functional theory (DFT) calculations reveal that Ni/Ni(OH)₂ heterostructure, although partially reduced, can still persist during HER catalysis and it is the Ni–Ni(OH)₂ interface reducing the energy barrier of H1 adsorption thus promoting the HER performance.     

TiO2/MXene-Assisted LDI-MS for Urine Metabolic Profiling in Urinary Disease

Cancer remains an intractable medical problem. Rapid diagnosis and identification of cancer are critical to differentiate it from nonmalignant diseases. High-throughput biofluid metabolic analysis has potential for cancer diagnosis. Nevertheless, the present metabolite analysis method does not meet the demand for high-throughput screening of diseases. Herein, a high-throughput, cost-effective, and noninvasive urine metabolic profiling method based on TiO₂/MXene-assisted laser desorption/ionization mass spectrometry (LDI-MS) is presented for the efficient screening of bladder cancer (BC) and nonmalignant urinary disease. Combined with machine learning, TiO₂/MXene-assisted LDI-MS enables high diagnostic accuracy (96.8%) for the classification of patient groups (including 47 BC and 46 ureteral calculus (UC) patients) from healthy controls (113 cases). In addition, BC patients can also be identified from noncancerous UC individuals with an accuracy of 88.3% in the independent test cohort. Furthermore, metabolite variations between BC and UC individuals are investigated based on relative quantification, and related pathways are also discussed. These results suggest that this method, based on urine metabolic patterns, provides a potential tool for rapidly distinguishing urinary diseases and it may pave the way for precision medicine.     

Fabrication and characterizations of Cr3+-doped ZnGa2O4 transparent ceramics with persistent luminescence

0.5 at.% Cr:ZnGa₂O₄ precursor was synthesized by the co-precipitation method with nitrates as raw materials, using ammonium carbonate as the precipitant. Low-agglomerated Cr:ZnGa₂O₄ powders with an average particle size of 43 nm were obtained by calcining the precursor at 900℃ for 4 h. Using the powders as starting materials, 0.5 at.% Cr:ZnGa₂O₄ ceramics with an average grain size of about 515 nm were prepared by presintering at 1150℃ for 5 h in air and HIP post-treatment at 1100℃ for 3 h under 200 MPa Ar. The in-line transmittance of 0.5 at.% Cr:ZnGa₂O₄ ceramics with a thickness of 1.3 mm reaches 59.5% at the wavelength of 700 nm. The Cr:ZnGa₂O₄ ceramics can be effectively excited by visible light and produce persistent luminescence at 700 nm. For Cr:ZnGa₂O₄ transparent ceramics, the brightness of afterglow was larger than 0.32 mcd/m² after 30 min, which is far superior to that of Cr:ZnGa₂O₄ persistent luminescence powders.     

Adaptive compensation of persistent actuator failures of nonlinear systems

In this article, adaptive compensation designs are developed for nonlinear systems with uncertainties from the system functions and persistent actuator failures of characterizations that (i) some unknown system inputs are stuck at some unknown fixed or varying values at unknown time instants and (ii) the failure pattern always switches from one to another and the switching does not stop. Such a controlled plant is described by an uncertain time-varying nonlinear system, and some robust adaptive feedback linearization based failure compensation results are studied for closed-loop system stabilization and bounded output tracking for some specific conditions. To improve the tracking performance in the presence of persistent actuator failures, a new adaptive control scheme is developed, using the failure indicator function which contains the failure pattern and failure time in the formulation. Detailed stability and tracking performance are shown. Simulation results are shown to verify the effectiveness of the proposed adaptive actuator failure compensation method.     

Structural,optical and electrical properties of indium doped Cu2ZnSn(S,Se)4 thin films synthesized by the DC and RF reactive magnetron cosputtering

Element doping into the Cu₂ZnSn(S,Se)₄ (CZTSSe) absorber is an effective method to optimize the performance of thin film solar cells. In this study, the Cu₂In_xZn_1-xSn(S,Se)₄ (CIZTSSe) precursor film was deposited by magnetron cosputtering technique using indium (In) and quaternary Cu₂ZnSnS₄ (CZTS) as targets. Meanwhile, the In content was controlled using the direct current (DC) power on In target (P_In). A single kesterite CIZTSSe alloy was formed by successfully doping a small number of In³⁺ into the main lattice of CZTSSe. The partial Zn²⁺ cations were substituted by In³⁺ ions, resulting in improving properties of CZTSSe films. Morphological analysis showed that large grain CIZTSSe films could be obtained by doping In. The well-distributed, smooth, and dense film was obtained when the P_In was 30 W. The band gap of CIZTSSe could be continuously adjusted from 1.27 to 1.05 eV as P_In increased from 0 to 40 W. In addition, the CIZTSSe alloy thin film at P_In = 30 W exhibited the best p-type conductivity with Hall mobility of 6.87 cm²V^?1s^?1, which is a potential material as the absorption layer of high-performance solar cells.     

Combining molybdenum carbide with ceria overlayers to boost Mo/CeO2 catalyzed ammonia synthesis

The design of an efficient non-noble metal catalyst is of burgeoning interest for ammonia synthesis. Herein, we report a Mo₂C/CeO₂ catalyst that is superior in ammonia synthesis activity. In this catalyst, molybdenum carbide coexisted with the ceria overlayers which is from the ceria support as the strong metal–support interaction. There is a high proportion of low-valent Mo species, as well as high concentration of Ce³⁺ and surface oxygen species. The presence of Mo₂C and CeO₂ overlayers not only leads to enhancement of hydrogen and nitrogen adsorption, but also facilitates the desorption and exchange of adsorbed species with the gaseous reagents. Compared with the Mo/CeO₂ catalyst prepared without carbonization, the Mo₂C/CeO₂ catalyst is more than sevenfold higher in ammonia synthesis rate. This work not only presents an explicit example of designing Mo-based catalyst that is highly efficient for ammonia synthesis by tuning the adsorption and desorption properties of the reactant gases, but opens a perspective for other elements in ammonia synthesis.     

PIXE study on recovery of making-technology of Chinese Longquan celadon made in the Southern Song Dynasty (1127–1279 CE)

Proton induced X-ray emission (PIXE) technique and factor analysis were used to study the recovery of making-technology of Chinese Longquan celadon made in the late Southern Song Dynasty (1127–1279 CE). Based on factor analysis, for the raw material for body and the recipe for glaze, there is a close but slightly different relationship between these Longquan celadons unearthed from the core area of Dayao and the non-core area, despite all the Longquan celadons belong to the high-calcium-glaze system. The chemical compositions of most of the tentative body and glaze samples are very close to those of Longquan celadons unearthed from the core area of Dayao and the non-core area. This study can provide a guidance for recovery of making-technology of Longquan celandon.     

Deep Integration of Innovation and Entrepreneurship (InE) Education in Chinese University Classrooms

Recently, InE has been regarded as a popular education strategy in Chinese universities. However, problems have been exposed in the adoption of InE, for example, in InE courses and competitions. The purpose of this paper is to provide a possible solution to the problems, which is to organize effective InE courses by integrating InE with Inter-Course-level Problem-Based Learning (ICPBL). A detailed case is demonstrated by an ICPBL elective course design with deep integration of InE in the teaching, learning, and assessments. This paper contributes to a new curriculum design for promoting InE education in practically for Chinese universities.