自支撑过渡金属海水电解析氧催化剂研究进展

海水电解是一种很有前景的可持续绿氢生产技术。然而,由于受到缓慢的动力学、阳极上竞争性的氯释放反应、氯离子腐蚀和电极表面中毒等的影响,致使阳极材料的性能和耐久性下降,析氧反应(OER)的选择性降低。与传统的粉末催化剂相比,自支撑纳米阵列材料具有较低的界面电阻、较大的活性表面和优异的稳定性,已成为先进的催化剂。特别是在需要高电流密度的实际大规模制氢应用中,自支撑催化剂比粉末催化剂更具优势。电解过程中,在电极表面所产生气泡的强烈冲击下,粉末状纳米材料很容易剥离,导致催化活性降低,甚至频繁更换催化剂。相比之下,自支撑纳米材料的活性物质和基底之间具有很强的粘附性,确保了良好的电子导电性和高机械稳定性,有利于长期和循环使用。本文综述了用于海水电解自支撑过渡金属催化剂的最新进展,包括(氧)氢氧化物、氮化物、磷化物、硫族化物等。为确保OER过程中的高活性和高选择性,着重总结了各析氧催化剂在应对耐腐蚀性和屏蔽竞争反应方面所采取的策略。通常,构建具有高孔隙率和粗糙度的3D多孔纳米结构可以使催化剂具有较大的表面积和丰富的活性位点,是提高传质、OER活性和催化效率的有效策略。其次,催化剂表面的Cl−阻挡层,特别是兼具催化活性和保护作用的保护层,可以有效抑制Cl−的竞争性氧化和腐蚀,提高催化剂的催化活性、选择性和稳定性。此外,设计具有超亲水和超疏水表面的催化材料,以增加电解质的渗透性,促进活性位点的有效利用,并避免大量气泡的积累。最后,简要总结了OER催化剂在海水电解中的发展前景及建议。具体来说,海水电解的介质应从模拟盐水转移到天然海水中。鉴于天然海水电解中面临的诸多挑战,除了设计和合成具有高活性、高选择性和高稳定性的自支撑催化剂外,开发简单、低成本的天然海水预处理技术以最大限度地减少腐蚀和中毒问题也是海水电解未来发展的重要课题。更重要的是,应合理构建自支撑OER电催化剂的标准化评价体系。评估过程中应充分考虑催化剂内在活性、可达活性位点密度、尺寸、质量负荷、基质效应和试验条件等因素。

Geometry and tectonic deformation of the seismogenic structure for the 8 August 2017 M_S 7.0 Jiuzhaigou earthquake sequence,northern Sichuan, China

To reveal the geometry of the seismogenic structure of the Aug. 8, 2017 M_S 7.0 Jiuzhaigou earthquake in northern Sichuan,data from the regional seismic network from the time of the main event to Oct. 31, 2017 were used to relocate the earthquake sequence by the tomoDD program, and the focal mechanism solutions and centroid depths of the M_L ≥ 3.5 events in the sequence were determined using the CAP waveform inversion method. Further, the segmental tectonic deformation characteristics of the seismogenic faults were analyzed preliminarily by using strain rosettes and areal strains(As). The results indicate:(1) The relocated M_S 7.0 Jiuzhaigou earthquake sequence displays a narrow ～ 38 km long NNW-SSE-trending zone between the NW-striking Tazang Fault and the nearly NSstriking Minjiang Fault, two branches of the East Kunlun Fault Zone. The spatial distribution of the sequence is narrow and deep for the southern segment, and relatively wide and shallow for the northern segment. The initial rupture depth of the mainshock is 12.5 km, the dominant depth range of the aftershock sequence is between 0 and 10 km with an average depth of 6.7 km. The mainshock epicenter is located in the middle of the aftershock region, showing a bilateral rupture behavior. The centroid depths of 32 M_L ≥ 3.5 events range from 3 to 12 km with a mean of about 7.3 km, consistent with the predominant focal depth of the whole sequence.(2) The geometric structure of the seismogenic fault on the southern section of the aftershock area(south of the mainshock) is relatively simple, with overall strike of ～150° and dip angle ～75°, but the dip angle and dip-orientation exhibit some variation along the segment. The seismogenic structure on the northern segment is more complicated; several faults, including the Minjiang Fault, may be responsible for the aftershock activities. The overall strike of this section is ～159° and dip angle is ～59°, illustrating a certain clockwise rotation and a smaller dip angle than the southern segment. The differences between the two segments demonstrate variation of the geometric structure along the seismogenic faults.(3) The focal mechanism solutions of 32 M_L ≥ 3.5 events in the earthquake sequence have obvious segmental characteristics. Strike-slip earthquakes are dominant on the southern segment, while 50% of events on the northern segment are thrusting and oblique thrusting earthquakes, revealing significant differences in the kinematic features of the seismogenic faults between the two segments.(4) The strain rosettes for the mainshock and the entire sequence of 31 M_L ≥ 3.5 aftershocks correspond to strike-slip type with NWW-SEE compressional white lobes and NNE-SSW extensional black lobes of nearly similar size. The strain rosette and As value of the entire sequence of 22 M_L ≥ 3.5 events on the southern segment are the same as those of the M_S 7.0 mainshock,indicating that the tectonic deformation here is strike-slip. However, the strain rosette of the entire sequence of 10 M_L ≥ 3.5 events on the northern segment show prominent white compressional lobes and small black extensional lobes, and the related As value is up to 0.52,indicating that the tectonic deformation of this segment is oblique thrusting with a certain strike-slip component. Differences between the two segments all reveal distinctly obvious segmental characteristics of the tectonic deformation of the seismogenic faults for the Jiuzhaigou earthquake sequence.

Three dimensional velocity structure and accurate earthquake location in Changning–Gongxian area of southeast Sichuan

In order to understand the crustal structure and tectonic background of the Changning–Gongxiang area, southeastern Sichuan Province, where a series of moderate-to-strong earthquakes occurred in recent years, we utilized the seismic phase data both from a local dense array and from the regional seismic networks;we used the tomoDD program to invert for the high-resolution three-dimensional velocity structure within the depth range of 0–10 km and for accurate hypocentral locations in this area. We analyzed the seismogenic structures for the events of Xingwen M5.7 in 2018 and Gongxian M5.3 and Changning M6.0 in 2019. The results show that:(1) widespread lateral inhomogeneity exists in the velocity structure of the study area, and the location of the velocity anomaly is largely consistent with known structures. In the range of distinguishable depth, the inhomogeneity decreases with increasing depth, and the velocity structure anomalies in some areas are continuous in depth;(2) earthquakes occurred in clusters, showing the characteristics of zonal folding trends in the NW-SE and NE-SW directions;the focal depth in the area is generally shallow in both the sedimentary cap and the crystalline basement. The seismogenic structures of small earthquake clusters are different in size and occurrence in different sections, and the clusters occurred mostly in regions with high P-or S-wave velocities;(3) synthesis of a variety of data suggests that the seismogenic structures of the Xingwen M5.7 and Changning M6.0 earthquakes are associated with slip faults that trend NW-SE in, respectively, the south wing and the axis of the Changning–Shuanghe anticline, while that of the Gongxian M5.3 earthquake is associated with thrust faults that trend N-S in the Jianwu syncline region. The dynamic sources of the three earthquakes are all from the SE pushing of the Qinghai–Tibet block on the Sichuan basin;(4) the risk of future strong earthquakes in this area must be reevaluated in light of the facts(a)that in recent years, moderate-to-strong earthquake swarms have occurred frequently in southeast Sichuan;(b) that the complex structural area exhibits the easy-to-trigger characteristic, and(c) that the small-scale faults in this area are characterized by the phenomenon of stress "lock and release".

Carbon-Isotope Excursions Recorded in the Cambrian System,South China:Implications for Mass Extinctions and Sea-Level Fluctuations

Cambrian carbonates with abundant fossils of agnostoid trilobites deposited on the southern slope （Jiangnan slope belt） of the Yangtze Platform and in the Jiangnan deepwater basin are well exposed in the Wangeun Section of western Hunan, South China, and in the Duibian A Section of western Zhejiang, southeastern China, respectively. To better understand the response of carbonisotope excursions to depositional environment changes, mass extinctions and eustatic events, we collected 530 carbonate samples in fresh roadcut exposures of the two measured sections for analysis of carbon and oxygen isotopic compositions. Data of δ^13C from the Wangcun Section, western Hunan, South China, demonstrate that the Cambrian carbon-isotope profile includes three remarkable positive excursions CPEwc-1, 2, 3 in the Upper Series 2, in the Lower and in the Middle Furongian Series. Three distinctive negative excursions CNEwc,-1, 2, 3 were separately tested in the Lower Terreneuvian Series, Lower Series 3 and in the Upper Furongian Series. Similarly, in the corresponding horizons in the Duibian A Section, Zhejiang Province, southeastern China, three positive excursions CPEdb-1, 2, 3 and three negative excursions CNEdb-1, 2, 3 also have been discovered. We interpret these significant carbon-isotope excursions as being associated with enhanced biogenic prodnctivity, mass extinctions and eustatic events.

Carboniferous integrative stratigraphy and timescale of China

The Carboniferous period lasted about 60 Myr, from ～358.9 Ma to ～298.9 Ma. According to the International Commission on Stratigraphy, the Carboniferous System is subdivided into two subsystems, i.e., Mississippian and Pennsylvanian, including 6 series and 7 stages. The Global Stratotype Sections and Points(GSSPs) of three stages have been ratified, the Tournaisian, Visean, and Bashkirian stages. The GSSPs of the remaining four stages(i.e., the Serpukhovian, Moscovian,Kasimovian, and Gzhelian) have not been ratified so far. This paper outlines Carboniferous stratigraphic subdivision and correlation on the basis of detailed biostratigraphy mainly from South China, and summarizes the Carboniferous chronostratigraphic framework of China. High-resolution biostratigraphic study reveals 37 conodont zones, 24 foraminiferal(including fusulinid) zones, 13 ammonoid zones, 10 brachiopod zones, and 10 rugose coral zones in the Carboniferous of China. The biostratigraphic framework based on these biozones warrants the precise correlation of regional stratigraphy of China(including2 subsystems, 4 series, and 8 stages) to that of the other regions globally. Meanwhile, the Carboniferous chemo-, sequence-,cyclo-, and event-stratigraphy of China have been intensively studied and can also be correlated worldwide. Future studies on the Carboniferous in China should focus on(1) the correlation between shallow-and deep-water facies and between marine and continental facies,(2) high-resolution astronomical cyclostratigraphy, and(3) paleoenvironment and paleoclimate analysis based on geochemical proxies such as strontium and oxygen isotopes, as well as stomatal indices of fossil plants.