微分电化学质谱测定石墨在析氧反应中的结构腐蚀

电催化析氧反应(OER)不仅是电解水制氢的半反应,也是电催化二氧化碳还原、氮气还原、硝酸根还原、有机小分子还原、金属-空气电池的重要半反应。OER过程是通过四电子机制驱动的。由于OER自身缓慢而复杂的动力学及其自带的强氧化特性,研究电催化材料在OER中的氧化重构规律及其催化机制,对于提高析氧反应的效率意义重大。碳材料作为一类无金属电极材料广泛应用于电催化过程中,其价格低廉、储量丰富、活性、稳定性高,是一种有潜力的OER催化剂。碳材料表面的含氧官能团已被证明是OER的活性位点,但在更高的氧化电位下,由于缺乏对活性位点演化机制的认识,导致对碳材料OER性能的失活机制仍不清楚。正确识别出析氧条件下碳材料的活性位点已成为该领域的研究热点。然而,非原位的表征技术,如X射线衍射技术、扫描电子显微镜技术等难以反映碳材料在工作条件下的催化状态。因此,本文以石墨作为模型材料,利用微分电化学质谱(DEMS)探究石墨在OER过程中的结构变化,研究测试过程中外加电压和电解液pH值对石墨氧化的影响。结果表明,在酸性(pH 0)、中性(pH 7)和碱性(pH 14)条件下,高纯石墨片均是先发生自身的氧化并产生氧化官能团;随着电位的增加,酸性、中性和碱性环境中的石墨阳极均在1.6 V vs.可逆氢电极(RHE)产生CO_(2)和CO,且CO_(2)产量逐渐增大;在酸性条件下,O_(2)的生成电位高于CO_(2),而碱性条件则相反。因此,在碱性条件下,高纯石墨片在一定的电位区间下可以作为OER催化剂使用。本工作不仅揭示了碳材料在电化学氧化条件下全pH值范围内的结构转化规律和相应的演化产物,也提出了碳材料作为OER催化剂时可行的电位操作区间。

The variation in basal channels and basal melt rates of Pine Island Ice Shelf

In recent years,there has been a significant acceleration in the thinning,calving and retreat of the Pine Island Ice Shelf(PIIS).The basal channels,results of enhanced basal melting,have the potential to significantly impact the stability of the PIIS.In this study,we used a variety of remote sensing data,including Landsat,REMA DEM,ICESat-1 and ICESat-2 satellite altimetry observations,and Ice Bridge airborne measurements,to study the spatiotemporal changes in the basal channels from 2003 to 2020 and basal melt rate from 2010 to 2017 of the PIIS under the Eulerian framework.We found that the basal channels are highly developed in the PIIS,with a total length exceeding 450 km.Most of the basal channels are ocean-sourced or groundingline-sourced basal channels,caused by the rapid melting under the ice shelf or near the groundingline.A raised seabed prevented warm water intrusion into the eastern branch of the PIIS,resulting in a lower basal melt rate in that area.In contrast,a deepsea trough facilitates warm seawater into the mainstream and the western branch of the PIIS,resulting in a higher basal melt rate in the main-stream,and the surface elevation changes above the basal channels of the mainstream and western branch are more significant.The El Ni?o event in 2015–2016 possibly slowed down the basal melting of the PIIS by modulating wind field,surface sea temperature and depth seawater temperature.Ocean and atmospheric changes were driven by El Ni?o,which can further explain and confirm the changes in the basal melting of the PIIS.

Determining topographic shielding from digital elevation models for cosmogenic nuclide analysis: a GIS model for discrete sample sites

Topographic shielding(TS) is an important factor in cosmogenic nuclide surface exposure dating. The development of geographic information systems(GIS) and the availability of digital elevation models(DEMs) make it possible to derive this factor directly from a DEM. Most available GIS models derive the TS factors for an area(all cells in a DEM) without the consideration of surface conditions of individual sites, such as the strike, dip,and height above ground, into the calculation. This paper presents a new GIS model to derive the TS factors for discrete sample sites. This model uses the Skyline and Skyline Graph functions in ArcGIS to extract the set of azimuth and elevation angles of topographic obstructions around each site from a DEM(considering the sample height above ground)and then incorporates the strike and dip information of the sample surface to derive the TS factor. All processing tools and steps are streamlined in ArcGIS modelbuilder and this model can be run like a standard ArcGIS geoprocessing tool. It provides an easy and user-friendly means to derive the TS factors for discrete samples based on a DEM and the measured strike, dip and sample height for each site.

Evaluation and Validation of Recent Freely-Available ASTER-GDEM V.2, SRTM V.4.1 and the DEM Derived from Topographical Map over SW Grombalia (Test Area) in North East of Tunisia

Digital Elevation Models (DEMs) provide one of the most useful digital datasets for a wide range of users. Both the Shuttle Radar Topographic Mission (STRM V.4.1) topography and the Advanced Spaceborne Thermal Emission and Reflection Radiometer Global Digital Elevation Model (ASTER-GDEM V.2) have been widely used in geomorphology, hydrology, tectonic, and others since they were made access to the public. The magnitude of vertical errors of two near-global DEMs—SRTM and ASTER-GDEM is compared and validated against a reference DEM which has a relatively high precision of 1:25,000 scale constructed from topographical map. Moreover, the reference DEM, ASTER-GDEM and SRTM were used as basic topographic data to extract some Morphometric index. The parameters like slope and shaded reflectance maps, were derived from the elevation distribution to provide a more sensitive indication of DEM quality. A square area in the North East of Tunisia was selected as a case study to test and evaluate the elevation accuracy of ASTER-GDEM and SRTM. The relative accuracy approach and absolute accuracy were adopted to evaluate global DEMs. The comparisons show that SRTM overestimates and ASTER-GDEM underestimates elevations, both DEMs can be used to extract the elevations of required geometric data,?i.e.?sub watershed boundaries, drainage information and cross sections. However, small errors still exist in. The lower root mean square errors values indicate that SRTM is comparatively more accurate than ASTER-GDEM.