Heteroatom Coordination Regulates Iron Single-Atom-Catalyst with Superior Oxygen Reduction Reaction Performance for Aqueous Zn-Air Battery.

Platinum group metal (PGM)-free M-N-C catalysts have exhibited dramatic electrocatalytic performance and are considered the most promising candidate of the Pt catalysts in oxygen reduction reaction (ORR). However, the electrocatalytic performance of the M-N-C catalysts is still limited by their inferior intrinsic activity and finite active site density. Regulating the coordination environment and increasing the pore structure of the catalyst is an effective strategy to enhance the electrocatalytic performance of the M-N-C catalysts. In this work, the coordination environment and pore structure exquisitely regulated Fe-N-C catalyst exhibit excellent ORR activity and durability. With the enhanced intrinsic activity and increased active site density, the optimized Fe-N/S-C catalyst shows impressive ORR activity (E1/2  = 0.904 V vs reversible hydrogen electrode (RHE)) and superior long-term durability in an alkaline medium. As the advanced physical characterization and theoretical chemistry methods illustrate, the S-modified Fe-Nx (Fe-N3 /S-C) moiety is confirmed as the improved active center for ORR, and the increased active site density further improved ORR efficiency. Based on the Fe-N/S-C cathode, a Zn-air battery is fabricated and shows superior power density (315.4 mW cm-2 ) and long-term discharge stability at 20 mA cm-2 . This work would open a new perspective to design atomically dispersed iron-metal site catalysts for advanced electro-catalysis.

Defect-engineered Sulfur Vacancy Modified NiCo2 S4-x Nanosheet Anchoring Polysulfide for Improved Lithium Sulfur Batteries.

The low conductivity of sulfur and the shuttle effect of lithium polysulfides (LiPSs) are the two intrinsic obstacles that limit the application of lithium-sulfur batteries (LSBs). Herein, a sulfur vacancy introduced NiCo2 S4 nanosheet array grown on carbon nanofiber (CNF) membrane (NiCo2 S4-x /CNF) is proposed to serve as a self-supporting and binder-free interlayer in LSBs. The conductive CNF skeleton with a non-woven structure can effectively reduce the resistance of the cathode and accommodate volume expansion during charge-discharge process. The bonding between CNF matrix and NiCo2 S4 nanosheet is enhanced by in situ growth, ensuring fast electron transfer. Besides, the sulfur vacancies in NiCo2 S4 enhance the chemisorption of LiPSs, and the highly active sites at vacancies can accelerate the LiPSs conversion kinetics. LSB paired with NiCo2 S4-x /CNF interlayer achieved improved stability in 500 cycles at 0.2 C and long life of 3000 cycles at 3 C. More importantly, a high areal capacity of 9.69 mAh cm-2 is achieved with a sulfur loading of 10.8 mg cm-2 and a low electrolyte to sulfur (E/S) ratio of 4.8. This work provides insight into the sulfur vacancy in catalysis design for LiPSs conversion and demonstrates a promising direction for electronic defect engineering in material design for LSBs.

Advances in Transition-Metal-Based Dual-Atom Oxygen Electrocatalysts.

Oxygen electrocatalysis has aroused considerable interest over the past years because of the new energy technologies boom in hydrogen energy and metal-air battery. However, due to the sluggish kinetic of the four-electron transfer process in oxygen reduction reaction and oxygen evolution reaction, the electro-catalysts are urgently needed to accelerate the oxygen electrocatalysis. Benefit from the high atom utilization efficiency, unprecedentedly high catalytic activity, and selectivity, single-atom catalysts (SACs) are considered the most promising candidate to replace the traditional Pt-group-metal catalysts. Compared with SACs, the dual-atom catalysts (DACs) are attracting more attraction including higher metal loading, more versatile active sites, and excellent catalytic activity. Therefore, it is essential to explore the new universal methods approaching to the preparation, characterization, and to elucidate the catalytic mechanisms of the DACs. In this review, several general synthetic strategies and structural characterization methods of DACs are introduced and the involved oxygen catalytic mechanisms are discussed. Moreover, the state-of-the-art electrocatalytic applications including fuel cells, metal-air batteries, and water splitting have been sorted out at present. The authors hope this review has given some insights and inspiration to the researches about DACs in electro-catalysis.

Defect-Rich Single Atom Catalyst Enhanced Polysulfide Conversion Kinetics to Upgrade Performance of Li-S Batteries.

Lithium-sulfur (Li-S) batteries have attracted considerable attention owing to their extremely high energy densities. However, the application of Li-S batteries has been limited by low sulfur utilization, poor cycle stability, and low rate capability. Accelerating the rapid transformation of polysulfides is an effective approach for addressing these obstacles. In this study, a defect-rich single-atom catalytic material (Fe-N4/DCS) is designed. The abundantly defective environment is favorable for the uniform dispersion and stable existence of single-atom Fe, which not only improves the utilization of single-atom Fe but also efficiently adsorbs polysulfides and catalyzes the rapid transformation of polysulfides. To fully exploit the catalytic activity, catalytic materials are used to modify the routine separator (Fe-N4 /DCS/PP). Density functional theory and in situ Raman spectroscopy are used to demonstrate that Fe-N4 /DCS can effectively inhibit the shuttling of polysulfides and accelerate the redox reaction. Consequently, the Li-S battery with the modified separator achieves an ultralong cycle life (a capacity decay rate of only 0.03% per cycle at a current of 2 C after 800 cycles), and an excellent rate capability (894 mAh g-1 at 3 C). Even at a high sulfur loading of 5.51 mg cm-2 at 0.2 C, the reversible areal capacity still reaches 5.4 mAh cm-2 .

A Highly Efficient Sulfur Host Enabled by Nitrogen/Oxygen Dual-Doped Honeycomb-Like Carbon for Advanced Lithium-Sulfur Batteries.

High energy density and long cycle life of lithium-sulfur (Li-S) batteries suffer from the shuttle/expansion effect. Sufficient sulfur storage space, local fixation of polysulfides, and outstanding electrical conductivity are crucial for a robust cathode host. Herein, a modified template method is proposed to synthesize a highly regular and uniform nitrogen/oxygen dual-doped honeycomb-like carbon as sulfur host (N/O-HC-S). The unique structure not only offers physical entrapment for polysulfides (LiPSs) but also provides chemical adsorption and catalytic conversion sites of polysulfides. In addition, this structure offers enough space for loading sulfur, and a regular space of nanometer size can effectively prevent sulfur particles from accumulating. As expected, the as-prepared N/O-HC900-S with high areal sulfur loading (7.4 mg cm-2 ) shows a high areal specific capacity of 7.35 mAh cm-2 at 0.2 C. Theoretical calculations also reveal that the strong chemical immobilization and catalytic conversion of LiPSs attributed to the spin density and charge distribution of carbon atoms will be influenced by the neighbor nitrogen/oxygen dopants. This structure that provides cooperative chemical adsorption, high lithium ions flux, and catalytic conversion for LiPSs can offer a new strategy for constructing a polysulfide confinement structure to achieve robust Li-S batteries.

Factors that affect the duration of wearing disposable personal protective equipment by healthcare professionals in Wuhan during treatment of COVID-19 patients: An epidemiological study.

The purpose of this study of healthcare workers who cared for COVID-19 patients was to identify factors that affected the duration of wearing personal protective equipment (PPE). The results of this study will provide initial guidance to practicing clinicians and a foundation for further research on this topic. This cross-sectional study examined 139 frontline healthcare professionals who worked at a single hospital in Wuhan, China, from March 16 to April 1, 2020. General and demographic data, physical and mental status, use of personal protective equipment, type of hospital work, and duration of wearing personal protective equipment were recorded. The mean duration of wearing personal protective equipment was 194.17 min (standard deviation: 3.71). Multiple linear regression analysis indicated that the duration of wearing personal protective equipment was significantly associated with the presence of a chronic disease, working hours when feeling discomfort, lack of patient cooperation and subsequent psychological pressure, prolonged continuous wearing of personal protective equipment, feeling anxious about physical strength, and the presence of fatigue when wearing personal protective equipment. These factors should be considered by practicing healthcare professionals and in future studies that examine the optimal duration of wearing personal protective equipment.

Enhanced Structural Stability of Nickel-Cobalt Hydroxide via Intrinsic Pillar Effect of Metaborate for High-Power and Long-Life Supercapacitor Electrodes.

Layered α-Ni(OH)2 and its derivative bimetallic hydroxides (e.g., α-(Ni/Co)(OH)2) have attracted much attention due to their high specific capacitance, although their insufficient cycling stability has blocked their wide application in various technologies. In this work, we demonstrate that the cycling performance of α-(Ni/Co)(OH)2 can be obviously enhanced via the intrinsic pillar effect of metaborate. Combining the high porosity feature of the metaborate stabilized α-(Ni/Co)(OH)2 and the improved electronic conductivity offered by graphene substrate, the average capacitance fading rate of the metaborate stabilized α-(Ni/Co)(OH)2 is only ∼0.0017% per cycle within 10 000 cycles at the current density of 5 A g-1. The rate performance is excellent over a wide temperature range from -20 to 40 °C. We believe that the enhancements should mainly be ascribed to the excellent structural stability offered by the metaborate pillars, and the detailed mechanism is discussed.

Quartz-Enhanced Photoacoustic Spectroscopy with Right-Angle Prism.

A right-angle prism was used to enhance the acoustic signal of a quartz-enhanced photoacoustic spectroscopy (QEPAS) system. The incident laser beam was parallelly inverted by the right-angle prism and passed through the gap between two tuning fork prongs again to produce another acoustic excitation. Correspondingly, two pairs of rigid metal tubes were used as acoustic resonators with resonance enhancement factors of 16 and 12, respectively. The QEPAS signal was enhanced by a factor of 22.4 compared with the original signal, which was acquired without resonators or a prism. In addition, the system noise was reduced a little with double resonators due to the Q factor decrease. The signal-to-noise ratio (SNR) was greatly improved. Additionally, a normalized noise equivalent absorption coefficient (NNEA) of 5.8 × 10(-8) W·cm(-1)·Hz(-1/2) was achieved for water vapor detection in the atmosphere.

Preparation and Growth of N-Doped Hollow Carbon Nanospheres and Their Application as Catalyst Support in Direct Borohydride Fuel Cell.

N-doped hollow carbon nanospheres (HCNSs) were prepared by electric arc discharge method in N2 atmosphere. X-ray Photoelectron Spectroscopy (XPS) analysis shows that their nitrogen content reaches up to 4.9 atom%. Both the low thermal conductivity of N2 and the doping of nitrogen atom make carbon unit bend to form hollow nanosphere structure. High-resolution transmission electron microscopy (HRTEM) and X-ray diffusion (XRD) analysis prove the presence of detected defects and a poor crystallinity on the HCNSs shell. Moreover, annealing treatment of HCNSs was carried out at 1100 degrees C/10 h and 1400 degrees C/2 h to research their fracture extension. It is found that HCNSs could grow into closed-tubes even with a shell at high annealing temperature. HCNSs were applied in direct borohydride fuel cell (DBFC) to evaluate their catalytic performance. The electrochemical results show that pure HCNSs doesn't have any catalysis effect, but they can greatly promote the catalytic performance of CoO, and the largest polarization current density of which achieves 1.845 A x cm(-2) at -0.7 V (vs. Hg/HgO electrode).

Demodulation algorithm used in single-beam system immune to light power drift.

A demodulation algorithm based on the head-tail technique is proposed for single-beam water vapor detection under rough environmental conditions, which is immune to fluctuations of light power. In the head-tail technique, collected data are processed by adding the head and tail data together and gradually approaching the center. The majority of photocurrent attenuation caused by optical loss can be effectively compensated by combining an optical intensity normalization coefficient in the method. The experiment indicates that, when the light power attenuates 4%, the deviation in a single-beam system is 1.29%, which is obviously superior to a dual-beam subtraction system whose deviation is 8.45%. The connection and advantages compared to a previous single-beam detection system have been discussed. The whole arrangement is simply designed without a beam splitter, of which the reliability and validity are fully verified by the experimental results.

A Time Difference Method for Measurement of Phase Shift between Distributed Feedback Laser Diode (DFB-LD) Output Wavelength and Intensity.

A time difference method to conveniently measure the phase shift between output wavelength and intensity of distributed feedback laser diodes (DFB-LDs) was proposed. This approach takes advantage of asymmetric absorption positions at the same wavelength during wavelength increase and decrease tuning processes in the intensity-time curve by current modulation. For its practical implementation, a measurement example of phase shift was demonstrated by measuring a time difference between the first time and the second time attendances of the same gas absorption line in the intensity-time curve during one sine or triangle modulation circle. The phase shifts at modulation frequencies ranging from 50 Hz to 50 kHz were measured with a resolution of 0.001π. As the modulation frequency increased the shift value increased with a slowed growth rate.

Atomically Dispersed Dual-Metal ORR Catalyst with Hierarchical Porous Structure for Zn-Air Batteries.

The metal-nitrogen-carbon (M-N-C)-based catalysts are promising to replace PGM (platinum group metal) to accelerate oxygen reduction reaction due to their excellent electrocatalytic performance. However, the inferior intrinsic activity and poor active site density confining further improvement in their performance. Modulating the electronic structure and reasonably designing the pore structure are widely acknowledged effective strategies to boost the activity of the M-N-C catalysts. However, it is a great challenge to form abundant pores to regulate the electronic structure via the facile method. Herein, a hierarchical, porous dual-atom catalyst FeNi-NPC-1000 has been architectured by the Na2CO3 template method and bimetallic doping modification strategy. Benefitting from the optimized pore and electronic structure, the as-prepared FeNi-NPC-1000 possesses a high specific surface area (1412.8 m2 g-1) and improved ORR activity (E1/2 = 0.877 V vs RHE), which is superior to that of Pt/C (E1/2 = 0.867 V vs RHE). With the evidence of AC-STEM, XAS, and DFT, the FeNi-N8-C moiety is proven to be the key active site to realize high-efficiency ORR catalysis. When assembled it as an air cathode of ZABs, FeNi-NPC-1000 displays superior discharge performance (Pmax = 367.1 mW cm-2) and a stable battery long-life. This article will provide a new strategy for designing dual-metal atomic catalysts applied in metal-air batteries.

High-sensitive measurement of water vapor: shot-noise level performance via a noise canceller.

Taking advantages of distributed feedback laser diode a technique is described to achieve high-sensitive measurement for water vapor concentration. This technique, with a modified balanced ratio metric detection system, has improved the accuracy of measured absorption spectrum by two main aspects. Improvement by matching equivalent conductivity of signal or reference photo detector (PD) is presented, and with the additional matched resistance suppression for the power variation in the signal-beam has been improved from 53 to 88 dB. The importance of integrating amplifier bandwidth design from the circuit to the measured absorption spectrum has been demonstrated in our experiment. For a scan rate of 32 Hz with an optimal corresponding bandwidth of 15.9 kHz, the absorption spectrum is well described by Voigt profile, with a difference of 1% at an atmosphere pressure of 1 atm and a room temperature of 296 K. With the application of averaging and filtering, absorption sensitivity of 1.093×10(-6) for water vapor at 1368.597 nm has been demonstrated, and the corresponding concentration is 71.8 ppb in just a 10 cm path length.

Reliability analysis and comparison of demodulation methods for dual-beam wavelength-modulation spectroscopy water vapor detection.

Subtraction, division, and balanced ratiometric detection (BRD) are three extensively used demodulation methods for dual-beam wavelength-modulation trace gas detection. However, reliability comparisons among these methods under changing environmental conditions were rarely researched. In this paper, the influences of ambient temperature and bend loss of fibers are analyzed in detail, and the reliabilities of the subtraction, division, and BRD methods are quantitatively compared for the first time to our knowledge. When the ambient temperature is increased by 1°C, the deviation of the division method is only 0.29%, which obviously outperforms the subtraction method (2.90%) and the BRD method (0.55%). Furthermore, a concept, "power fluctuation rejection ratio," is introduced to compare the suppression effects of the subtraction, division, and BRD methods on the laser light source power fluctuation. The study results demonstrate that the division method provides better reliability when the ambient temperature or bending loss is varied. The validity and reliability are fully verified by the fact that the experimental results give good agreement with the theoretical simulation.

Anti-Shedding Nickel-Protection-Layer Boosting an Ultrahigh Loading Carbon Fiber@Co-NiSx Electrode to Deliver Superior Areal/Volumetric/Gravimetric Capacitance.

Challenges remain to show good capacitive performance while achieving high loadings of active materials for supercapacitors. Trying to realize this version, a nickel-protecting carbon fiber paper@Co-doped NiSx (Ni-CP@Co-NiSx) electrode with high specific gravimetric, areal, and volumetric capacitance is reported in this work. This free-standing electrode is prepared by an electroplating-hydrothermal-electroplating (EHE) three-step method to achieve a high loading of almost 26.7 mg cm-2. The cobalt-doping and nickel-protection strategies effectively decrease the impedance and inhibit the active material dropping from the electrode resulting from the expansion stress, which endows the Ni-CP@Co-NiSx electrode with a high rate and good cycling performance, especially with an ultrahigh specific areal/volumetric/gravimetric capacitance of 53.3 F cm-2/2807 F cm-3/1997 F g-1 at 5 mA cm-2, respectively. Employing activated carbon functionalized with riboflavin (AC/VB2) as a negative electrode, the asymmetric supercapacitor device delivers a very high energy density of up to 60.4 W h kg-1. This work demonstrates that electrodes with a high loading density and excellent performance can be obtained by the combination of the EHE method to adjust the internal conductivity and external structural stability.

Tin disulfide embedded on porous carbon spheres for accelerating polysulfide conversion kinetics toward lithium-sulfur batteries.

Lithium-sulfur (Li-S) batteries are considered promising candidates for next-generation advanced energy storage systems due to their high theoretical capacity, low cost and environmental friendliness. However, the severe shuttle effect and weak redox reaction severely restrict the practical application of Li-S batteries. Herein, a functional catalytic material of tin disulfide on porous carbon spheres (SnS2@CS) is designed as a sulfur host and separator modifier for lithium-sulfur batteries. SnS2@CS with high electrical conductivity, high specific surface area and abundant active sites can not only effectively improve the electrochemical activity but also accelerate the capture/diffusion of polysulfides. Theoretical calculations and in situ Raman also demonstrate that SnS2@CS can efficiently adsorb and catalyse the rapid conversion of polysulfides. Based on these advantages, the SnS2@CS-based Li-S battery delivers an excellent reversible capacity of 868 mAh/g at 0.5C (capacity retention of 96 %), a high rate capability of 852 mAh/g at 2C, and a durable cycle life with an ultralow capacity decay rate of 0.029 % per cycle over 1000 cycles at 2C. This work combines the design of sulfur electrodes and the modification of separators, which provides an idea for practical applications of Li-S batteries in the future.

Effect of two surgical approaches on the lung function and prognosis of patients with combined esophagogastric cancer.

BACKGROUND: Adenocarcinoma of the esophagogastric junction has a center of origin within 5 cm of the esophagogastric junction. Surgical resection remains the main treatment. A transthoracic approach is recommended for Siewert I adenocarcinoma of the esophagogastric junction and a transabdominal approach is recommended for Siewert III adenocarcinoma of the esophagogastric junction. However, there is a need to determine the optimal surgical approach for Siewert II adenocarcinoma of the esophagogastric junction to improve lung function and the prognosis of patients. AIM: To investigate and compare the surgical effects, postoperative changes in pulmonary function, and prognoses of two approaches to treating combined esophagogastric cancer. METHODS: One hundred and thirty-eight patients with combined esophagogastric cancer treated by general and thoracic surgeries in our hospital were selected. They were divided into group A comprising 70 patients (transabdominal approach) and group B comprising 68 patients (transthoracic approach) based on the surgical approach. The indexes related to surgical trauma, number of removed lymph nodes, indexes of lung function before and after surgery, survival rate, and survival duration of the two groups were compared 3 years after surgery. RESULTS: The duration of surgery, length of hospital stay, and postoperative drainage duration of the patients in group A were shorter than those of the patients in group B, and the volume of blood loss caused by surgery was lower for group A than for group B (P < 0.05). At the one-month postoperative review, the first second, maximum ventilation volume, forceful lung volume, and lung volume values were higher for group A than for group B (P < 0.05). Preoperatively, the QLQ-OES18 scale scores of the patients in group A were higher than those in group B on re-evaluation at 3 mo postoperatively (P < 0.05). The surgical complication rate of the patients in group A was 10.00%, which was lower than that of patients in group B, which was 23.53% (P < 0.05). CONCLUSION: Transabdominal and transthoracic surgical approaches are comparable in treating combined esophagogastric cancer; however, the former results in lesser surgical trauma, milder changes in pulmonary function, and fewer complications.

Restriction of voltage decay by limiting low-voltage reduction in Li-rich oxide materials.

Li-rich layered oxides are recognized as promising candidates for next-generation Li-ion batteries owing to the high capacity of >250 mAh g-1, but the severe voltage fade has prevented their commercialization. It is widely known that high-voltage charge processes result in layered-to-spinel structural evolution and voltage fade in Li-rich layered oxides. This work emphasizes that limiting the low-voltage reduction can maintain the structure and voltage stability of Li-rich layered oxides after the 4.6 V high-voltage charge processes. A strategy of limiting the low-voltage (<2.8 V) reduction by cycling at 4.6-2.8 V was performed in traditional Li1.2Ni0.13Mn0.54Co0.13O2 and high-Ni Li1.2Ni0.222Mn0.504Co0.074O2. After 300 cycles, traditional Li1.2Ni0.13Mn0.54Co0.13O2 and high-Ni Li1.2Ni0.222Mn0.504Co0.074O2 cycling at 4.6-2 V showed midpoint discharge voltages of 2.83 V and 2.97 V with high voltage fade rates of 2.25 mV/cycle and 2.24 mV/cycle, respectively. While the two materials cycling at 4.6-2.8 V can maintain discharge midpoint voltages of 3.34 V and 3.49 V, with low voltage decay rates of 0.692 mV/cycle and 0.632 mV/cycle, respectively. To better understand the voltage performance, their electric structures were calculated by density functional theory. Physical characterizations were also used to analyze their differences in structural evolution. The results suggested that limiting low-voltage reduction in Li-rich layered oxides is highly necessary for maintaining their structure and voltage stability.

Enhanced electrochemical properties of potassium-doped lithium-rich oxide@carbon as cathode material for lithium-ion batteries.

Lithium-rich layered oxides are believed to be the most competitive cathode materials for next-generation lithium-ion batteries (LIBs) due to their high specific capacity, but the poor cycle stability and voltage attenuation severely limit their commercial applications. In this paper, a simple method combining surface treatment via pyrolysis of polyvinyl alcohol (PVA) and potassium ions (K+) doping, is designed to improve the above defects of the cobalt-free Lithium-rich material Li1.2Mn0.6Ni0.2O2 (LMR). The insoluble surface byproduct Li2CO3 and amorphous carbon nanolayer derived from the pyrolysis process of PVA alleviate the corrosion of acidic species with a favorable conductivity, while a large radius of K+ can enlarge the space of the lithium (Li) layer to facilitate the diffusion of Li+, suppress voltage polarization, and synchronously restrain the transformation from a layered structure to a spinel-like structure. After modification, the LMR material exhibits a great initial discharge capacity of 266.0 mAh g-1 at 0.1C, a remarkable rate capability of 159.1 mAh g-1 at 5C and an extremely high capacity retention of 98.5% over 200 cycles at 0.5C with a small voltage drop.

N,O-codoped carbon spheres with uniform mesoporous entangled Co3O4 nanoparticles as a highly efficient electrocatalyst for oxygen reduction in a Zn-air battery.

Highly efficient electrochemical catalysts for oxygen reduction reactions (ORRs) are urgently needed for various energy conversion and storage devices to overcome sluggish ORR kinetics. Here, N,O-codoped carbon spheres with uniform mesopores and a high specific surface area were used as supports for decorating Co3O4 nanoparticles via a facile immersion route. In addition to the benefit of ions and gas mass transfer, the abundant mesopores present in the three-dimensional (3D) carbon spheres also confine and isolate the Co3O4 nanoparticles growing in it, which help to provide rich Co3O4 active sites. The resulting hybrid material exhibits superior ORR activity in terms of even-better half-wave potential and stability than that of commercial Pt/C (40 wt%) in 0.1 M KOH electrolyte. To verify its catalytic activity, the hybrid material was employed as the cathode catalyst in a flexible solid-state zinc-air battery, which achieves a high power density of 227 mW cm-2; this power density is much higher than that of a Pt/C catalytic zinc-air battery (133 mW cm-2) under identical conditions. The improvement in catalytic activity in both aqueous and nonaqueous electrolytes can be attributed to the abundant active sites of the entangled Co3O4 nanoparticles, as well as the novel N,O-codoped carbon structure.