Ultralow charge-discharge voltage gap of 0.05 V in sunlight-responsive neutral aqueous Zn-air battery

Rechargeable neutral aqueous zinc-air batteries(ZABs)are a promising type of energy storage device with longer operating life and less corrosiveness compared with conventional alkaline ZABs.However,the neutral ZABs normally possess poor oxygen evolution reactions(OERs)and oxygen reduction reactions performance,resulting in a large charge–discharge voltage gap and low round-trip efficiency.Herein,we demonstrate a sunlight-assisted strategy for achieving an ultralow voltage gap of 0.05 V in neutral ZABs by using the FeOOH-decorated BiVO4(Fe-BiVO4)as an oxygen catalyst.Under sunlight,the electrons move from the valence band(VB)of Fe-BiVO_(4) to the conduction band producing holes in VB to promote the OER process and hence reduce the overpotential.Meanwhile,the photopotential generated by the Fe-BiVO_(4) compensates a part of the charging potential of neutral ZABs.Accordingly,the energy loss of the battery could be compensated via solar energy,leading to a record-low gap of 0.05 V between the charge and discharge voltage with a high round-trip efficiency of 94%.This work offers a simple but efficient pathway for solar-energy utilization in storage devices,further guiding the design of high energy efficiency of neutral aqueous ZABs.

Atomically Dispersed Transition Metal-Nitrogen-Carbon Bifunctional Oxygen Electrocatalysts for Zinc-Air Batteries:Recent Advances and Future Perspectives

Rechargeable zinc-air batteries(ZABs)are currently receiving extensive attention because of their extremely high theoretical specific energy density,low manufacturing costs,and environmental friendliness.Exploring bifunctional catalysts with high activity and stability to overcome sluggish kinetics of oxygen reduction reaction and oxygen evolution reaction is critical for the development of rechargeable ZABs.Atomically dispersed metal-nitrogen-carbon(M-N-C)catalysts possessing prominent advantages of high metal atom utilization and electrocatalytic activity are promising candidates to promote oxygen electrocatalysis.In this work,general principles for designing atomically dispersed M-N-C are reviewed.Then,strategies aiming at enhancing the bifunctional catalytic activity and stability are presented.Finally,the challenges and perspectives of M-N-C bifunctional oxygen catalysts for ZABs are outlined.It is expected that this review will provide insights into the targeted optimization of atomically dispersed M-N-C catalysts in rechargeable ZABs.

沸石咪唑基金属有机框架及其衍生材料用作锌-空气电池高效阴极催化剂的最新进展

清洁和可持续能源的大量应用和电动汽车行业的快速发展,为先进的储能/转换技术和设备带来了前所未有的机遇。可充电式锌-空气电池(ZAB)拥有的能量密度高、环境友好、安全性能高、成本低等优势,被广泛认为是最有前景的金属-空气电池之一。更重要的是,锌-空气电池所使用的锌资源丰富、价格便宜、能量密度适中以及还原潜力高。但由于在充电过程中空气阴极上氧还原反应的动力学过程十分缓慢,使得空气电池产生了相对大的超电势,也导致了ZAB无法实现商品化应用。沸石咪唑基金属有机框架(ZIFs)衍生的催化剂具有显著促进氧反应的能力。本文回顾了ZIFs衍生材料的最新进展,该材料可用作ZAB中的阴极催化剂。本文总结了一些主要的ZIFS衍生物材料在ZAB中的应用,包括了ZIFS衍生物的金属氮化物催化剂、ZIFs衍生物的金属氧化物催化剂、ZIFs衍生物的S/P/B掺杂催化剂和ZIFs衍生物的非金属碳催化剂等,还论述了这些ZIFs衍生物催化剂的结构特点。最后,阐明了研发用于ZAB的先进ZIFs衍生催化剂面临的挑战和一些观点。

Climate Change Impacts on Water Resources of Greater Zab River, Iraq

Greater Zab is the largest tributary of the Tigris River in lraq where the catchment area is currently being plagued by water scarcity and pollution problems. Contemporary studies have revealed that blue and green waters of the basin have been manifesting increasing variability contributing to more severe droughts and floods apparently due to climate change. In order to gain greater appreciation of the impacts of climate change on water resources in the study area in near and distant future, SWAT （Soil and Water Assessment Tool） has been used. The model is first tested for its suitability in capturing the basin characteristics, and then, forecasts from six GCMs （general circulation models） with about half-a-century lead time to 2046-2064 and one-century lead time to 2080-2100 are incorporated to evaluate the impacts of climate change on water resources under three emission scenarios： A 1 B, A2 and BI. The results showed worsening water resources regime into the future.

Heavy Metals Distribution and Their Correlation with Clay Size Fraction in Stream Sediments of the Lesser Zab River at Northeastern Iraq

Heavy metals (i.e. Cr, Co, Ni, Cu, Zn, Rb, Sr, Ba, Pb, V and Ga) distribution and their correlation with clay fraction were investigated. Fifteen samples of stream sediments were collected from the Lesser Zab River (LZR), which represent one of three major tributaries of the Tigris River at north-eastern Iraq. Grain size distributions and textural composition indicate that these sediments are mainly characterized as clayey silt and silty sand. This indicates that the fluctuation in the relative variation of the grain size distribution in the studied sediments is due local contrast in the hydrological conditions, such as stream speed, energy of transportation and geological, geomorphological and climatic characterizations that influenced sediments properties. On the other hand, clay mineral assemblages consist of palygorskite, kaolinite, illite, chlorite and smectite, which in turn reveals that these sediments were derived from rocks of similar mineralogical and chemical composition as it is coincided with other published works. The clay mineral assemblages demonstrate that major phase transformations were not observed except for the palygorskite formation from smectite, since the minerals pair exhibit good negative correlation (-0.598) within the Lesser Zab River (LZR) sediments. To determine interrelation between the heavy metals and the clay fractions in the studied samples, correlation coefficients and factor analysis were performed. Heavy metals provide significant positive correlation with themselves and with Al2O3, Fe2O3 and MnO. In addition, the results of factor analysis extracted two major factors;the first factor loading with the highest percent of variation (60%) from the major (Fe2O3, Al2O3 and MnO in weight %), heavy metals and clay fraction. While the second factor with the (14%) of variance includes Cr and silt fraction, which indicate the affinity of the heavy metals being adsorbed onto solid phase like clay particles. These observations suggest that a common mechanism regulates the heavy metal abundance, and that their concentrations are significantly controlled by fine clay fractions, clay mineral abundance and ferro manganese oxides-hydroxides.

Using GIS and Geostatistical Techniques for Mapping Piezometry and Groundwater Quality of the Albian Aquifer of the M’zab Region, Algerian Sahara

The M’zab region is subject to an arid Saharan climate where surface and sub-surface waters are of little importance. The Albian Aquifer, commonly called Continental Intercalary (CI), main component of North Western Sahara Aquifer System (NWSAS/SASS), constitutes the most extensive aquifer formation of the region. In our study area, the CI is identified, as a regional subset, as the Albian Aquifer of M’zab Region (AAMR). Its groundwater resources are considered the only source available to meet the growing needs of drinking water supply, agriculture and industry. This aquifer is heavily exploited by a very large number of wells (more than 750). Its supply is very low, so it is a very low renewable layer. This requires periodic monitoring and control of its piezometric level and its physico- chemical quality. The objective of our study is to know the current state of this aquifer, while studying the variation of its piezometry for the period 2010-2018, and also the chemical quality of its groundwater by analyzing more than 90 samples over the entire study area. The application of geostatistics by kriging and the steps of analysis, modelling and calculation of semivariogram have enabled us to draw up maps of the various hydrogeological and hydrochemical parameters. As a result, twelve thematic maps were gridded using Geostatistical tools of ArcGIS software. The water-level-change map showed a significant drop in the groundwater level over the entire M’zab region and especially around the major cities (Ghardaïa, Berriane, Metlili and Zelfana) with more than 8 meters. Chemical analyses of the Albian groundwater in the study area show the dominance of evaporite facies (Cl--Na+-Ca2+) with low concentrations than the Algerian Standards for Drinking (ASD). All the water quality indices (WQI) that have been mapped reveal that the groundwater samples were suitable for drinking and irrigation with a high quality of water located in the south of the study area.

Impact of Climate Change on Water Resources of Dokan Dam Watershed

Lesser Zab is one of the most important tributaries of Tigris River. During the last few decades, the streamflow significantly decreased for long periods followed by extensive flood in short periods. This study aimed to quantify the impact of climate change on streamflow at Dokan Dam until year 2050 using SWAT model based on the scenario of medium emission (A1B) and five climate projection models. SWAT run using Climate Forecasting System Reanalysis (CFSR) was used as weather input data then calibrated and validated on monthly time step for the period from 1980 to 2013 with Nash-Sutcliff Efficiency (NSE) of 0.73 and determination coefficient (R2) 0.73 for calibration processes. The data of this period is more reliable. The result indicated to a significant decrease on the projected streamflow until year 2050 with average streamflow for the six climate models of 167 m3/sec in past compared with the observed streamflow of 176.5 m3/sec for the base period (1980-2013). In addition, the study shows that most runoffs come from Iranian part of the Dokan Dam Watershed with 65% of total simulated runoff. It is highly recommended to improve the efficiency of water using for current and future water projects to meet the expected water shortage.

Assessment of Climate Change Impact on Water Resources of Lesser Zab, Kurdistan, Iraq Using SWAT Model

Kurdistan in northern Iraq, a semi-arid region, predominantly a pastureland, is nourished by Lesser Zab, which is the second major tributary of Tigris River. The discharge in the tributary, in recent times, has been experiencing increasing variability contributing to more severe droughts and floods supposedly due to climate change. For a proper appreciation, SWAT model has been used to assess the impact of climate change on its hydrological components for a half-centennial lead time to 2046-2064 and a centennial lead time to 2080-2100. The suitability of the model was first evaluated, and then, outputs from six GCMs were incorporated to evaluate the impacts of climate change on water resources under three emission scenarios: A1B, A2 and B1. The results showed worsening water resources regime.

伊朗西北部Zab盆地滑坡脆弱性

滑坡能对人类生活造成损害与破坏。对这些危害进行适当分析与模拟能够减低相关损失，甚至能够防止滑坡体移动。Zab河流盆地易受滑坡影响。为了评估研究区内的滑坡风险，使用了层次分析法（AHP）、地理信息系统（GIS）和局部数据。这些局部数据包括：边坡、边坡方位、到公路的距离、到排水网的距离、土地利用与土地覆盖、地质因素、地形特征以及研究区气候条件。利用AHP模型可提供显示滑坡初始脆弱性的真实区域图像。基于研究结果，确定南部盆地最易受滑坡影响。

Pd和Ru分别修饰Co_(3)O_(4)催化剂的制备及其高效氧催化性能研究

氧催化反应是决定燃料电池和金属-空气电池性能的重要组成部分,然而其反应的动力学滞后性严重制约着电池的发展。为改善氧催化性能,提出原位贵金属修饰策略,分别构筑了Pd修饰Co_(3)O_(4)(Pd-Co_(3)O_(4))和Ru修饰Co_(3)O_(4)(Ru-Co_(3)O_(4))催化剂。两种催化剂表现出独特的多孔结构,且实现了Pd/Ru纳米颗粒的高界面分散,有效提高了催化剂的传质和电化学活性面积,氧催化反应动力学得到了显著改善。此外,Pd-Co_(3)O_(4)的氧还原半波电位高达0.92 V,Ru-Co_(3)O_(4)在10 mA·cm^(-2)电流密度下的析氧电位低至1.55 V,表现出了优异的氧催化性能。基于Pd-Co_(3)O_(4)优异的氧还原催化性能和Ru-Co_(3)O_(4)优异的氧析出催化性能,将二者进行复合作为锌-空气电池(ZABs)氧电极的催化剂层。结果表明,复合催化剂组装的ZABs表现出了优异的电池性能,峰值功率密度高达118.5 mW·cm^(-2),优于Pt/C+RuO2复合催化剂。所报道的贵金属表面修饰策略为制备高贵金属利用率材料以及改善催化剂氧催化性能提供了新的思路方法。

FeCo-N encapsuled in nitrogen-doped carbon nanotubes as bifunctional electrocatalysts with a high stability for zinc air batteries

For zinc air batteries,a non-noble metal-based electrocatalyst with a high performance and stability in oxygen evolution reaction(OER)and oxygen reduction reaction(ORR)is imperative in application.Herein,a catalyst based on FeCo-N encapsuled in nitrogen-doped carbon nanotubes has been prepared,which provides an implementable method to design controlled structures with excellent bifunction al electrocatalytic activities.By adjusting the molar ratio of two metals,the synthesized FeCo-N-C catalyst delivers a competitive ORR and OER performance compared with commercial Pt/C and IrO_(2),performing a low overvoltage gap between ORR(E_(1/2))and OER(E_(j=10))of 0.8 V.Moreover,as a promising cathode in zinc air battery,the FeCo-N-C catalyst possesses an affirmative stability of over 100 h and large power density(129 mW·cm^(-2)).This work demonstrates that FeCo-N-C is one of the most promising catalysts for zinc air batteries and provides a possibility for exploration of batteries with high stability by adjusting the molar ratio of metals in the catalysts.

A novel composite(FMC)to serve as a durable 3D-clam-shaped bifunctional cathode catalyst for both primary and rechargeable zinc-air batteries

Novel and highly durable air cathode electrocatalyst with three dimensional （3D）-clam-shaped structure, MnO2 nanotubes-supported Fe2O3 （Fe2O3/MnO2） composited by carbon nanotubes （CNTs） （（Fe2O3/ MnO2）3/4-（CNTs）1/4） is synthesized using a facile hydrothermal process and a following direct heat- treatment in the air. The morphology and composition of this catalyst are analyzed using scanning elec- tronic microscopy （SEM）, transmission electron microscopy （TEM）, X-ray diffraction （XRD） and energy dispersive X-ray spectroscopy （EDX）. The morphology characteristics reveal that flower-like Fe2O3 parti- cles are highly dispersed on both MnO2 nanotubes and CNT surfaces, coupling all three components firmly. Electrochemical measurements indicate that the synergy of catalyst exhibit superior bi- functional catalytic activity for both oxygen reduction reaction （ORR） and oxygen evolution reaction （OER） as well as stability than Pt/C and lrO2 catalysts. Using these catalysts for air-cathodes, both primary and rechargeable zinc-air batteries （ZABs） are assembled for performance validation. In a primary ZAB, this 3D-clamed catalyst shows a decent open circuit voltage （OCV, -1.48 V） and a high discharge peak power density （349 mW cm 2）, corresponding to a coulomhic efficiency of 92%. In a rechargeahle ZABs with this bifunctional catalyst, high OCV （〉1.3 V） and small charge-discharge voltage gap （〈1.1 V） are achieved along with high specific capacity （780 mAh g 1 at 30 mA cm-2） and robust cycle-life （1,390 cycles at cycle profile of 20 mA/10 min）.

Specification and Verification of the Zab Protocol with TLA+

ZooKeeper Atomic Broadcast (Zab) is an atomic broadcast protocol specially designed for ZooKeeper, which supports additional crash recovery. This protocol actually has been widely adopted by famous Internet companies, but there are few studies on the correctness and credibility of the Zab protocol, and thus we utilize formal methods to study the correctness. In this paper, Zab, Paxos and Raft are all analyzed and compared to help better understand the Zab protocol. Then we model the Zab protocol with TLA+ and verify three properties abstracted from the specification by the model checker TLC, including two liveness properties and one safety property. The final experimental results can prove that the design of the protocol conforms to the original requirements. This paper makes up for the analysis of formal methods in the Zab protocol.