Tuning the electronic structure of a metal-organic framework for an efficient oxygen evolution reaction by introducing minor atomically dispersed ruthenium

The establishment of efficient oxygen evolution electrocatalysts is of great value but also challenging.Herein,a durable metal–organic framework(MOF)with minor atomically dispersed ruthenium and an optimized electronic structure is constructed as an efficient electrocatalyst.Significantly,the obtained NiRu_(0.08)-MOF with doping Ru only needs an overpotential of 187 mV at 10 mA cm^(-2) with a Tafel slop of 40 mV dec^(-1) in 0.1M KOH for the oxygen evolution reaction,and can work continuously for more than 300 h.Ultrahigh Ru mass activity is achieved,reaching 56.7 Ag^(-1)_(Ru) at an overpotential of 200 mV,which is 36 times higher than that of commercial RuO_(2).X-ray adsorption spectroscopy and density function theory calculations reveal that atomically dispersed ruthenium on metal sites in MOFs is expected to optimize the electronic structure of nickel sites,thus improving the conductivity of the catalyst and optimizing the adsorption energy of intermediates,resulting in significant optimization of electrocatalytic performance.This study could provide a new avenue for the design of efficient and stable MOF electrocatalysts.

Charge-transfer-regulated bimetal ferrocene-based organic frameworks for promoting electrocatalytic oxygen evolution

The ferrocene(Fc)-based metal-organic frameworks(MOFs)are regarded as compelling platforms for the construction of efficient and robust oxygen evolution reaction(OER)electrocatalysts due to their superior conductivity and flexible electronic structure.Herein,density functional theory simulations were addressed to predict the electronic structure regulations of CoFc-MOF by nickel doping,which demonstrated that the well-proposed CoNiFc-MOFs delivered a small energy barrier,promoted conductivity,and well-regulated d-band center.Inspired by these,a series of sea-urchin-like CoNiFc-MOFs were successfully synthesized via a facile solvothermal method.Moreover,the synchrotron X-ray and X-ray photoelectron spectroscopy measurements manifested that the introduction of nickel could tailor the electronic structure of the catalyst and induce the directional transfer of electrons,thus optimizing the rate-determining step of^(*)O→^(*)OOH during the OER process and yielding decent overpotentials of 209 and 252 mV at 10 and 200 mA cm^(−2),respectively,with a small Tafel slope of 39 mV dec^(−1).This work presents a new paradigm for developing highly efficient and durable MOF-based electrocatalysts for OER.

Micro-structural evolution and their effects on physical properties in different types of tectonically deformed coals

The macromolecular structure of tectonically deformed coals(TDC)may be determined by the deformation mechanisms of coal.Alterations of the macromolecular structure change the pore structure of TDC and thereby impact physical properties such as porosity and permeability.This study focuses on structure and properties of TDC from the Huaibei and Huainan coal mining areas of southern North China.Relationships between the macromolecular structure and the pore structure of TDC were analyzed using techniques such as X-ray diffraction,high-resolution transmission electron microcopy,and the low-temperature nitrogen adsorption.The results indicated that the directional stress condition can cause the arrangement of basic structural units(BSU)more serious and closer.And,the orientation is stronger in ductile deformed coal than in brittle deformed coal.Tectonic deformation directly influences the macromolecular structure of coal and consequently results in dynamic metamorphism.Because the size of BSU in brittle deformed coal increases more slowly than in ductile deformed coal,frictional heating and stress-chemistry of shearing areas might play a more important role,locally altering coal structure under stress,in brittle deformed coal.Strain energy is more significant in increasing the ductile deformation of coal.Furthermore,mesopores account for larger percentage of the nano-scale pore volume in brittle deformed coals,while mesopores volume in ductile deformed coal diminishes rapidly along with an increase in the proportion of micropores and sub-micropores.This research also approved that the deformations of macromolecular structures change nano-scale pore structures,which are very important for gas adsorption and pervasion space for gas.Therefore,the exploration and development potential of coal bed methane is promising for reservoirs that are subjected to a certain degree of brittle deformation(such as schistose structure coal,mortar structure coal and cataclastic structure coal).It also holds promise for TDC resulting from wrinkle structure coal of low ductile deformation and later superimposed by brittle deformation.Other kinds of TDC suffering from strong brittle-ductile and ductile deformation,such as scale structure coal and mylonitic structure coal,are difficult problems to resolve.

Crustal Structural and Tectonic Evolution and Oil Prospect Evaluation in the Songpan-Zoigê Block

Recent study of magnetotelluric （MT） inversion indicates that the basement of the Songpan- Zoige area could be a stable continental crust. There has developed quite thick and stable Paleozoic continental shelf margin-platform clastic and carbonate sediments during the Triassic. Preliminary field geologic investigation and hydrocarbon potential study show that good-quality source rocks, mainly argillaceous and carbonaceous shale, were deposited in the Cambrian and Silurian in this region, while diverse reservoirs of platform facies carbonate and clastic rocks were in the Carboniferous and Permian. The good vertical source-reservoir-seal configuration might indicate that there exists a certain potential for oil and gas exploration in this area.

Earthquake-related Tectonic Deformation of Soft-sediments and Its Constraints on Basin Tectonic Evolution

The authors introduced two kinds of newly found soft-sediment deformation-synsedimentary extension structure and syn-sedimentary compression structure, and discuss their origins and constraints on basin tectonic evolution. One representative of the syn-sedimentary extension structure is syn-sedimentary boudinage structure, while the typical example of the syn-sedimentary compression structure is compression sand pillows or compression wrinkles. The former shows NW-SE-trendlng contemporaneous extension events related to earthquakes in the rift basin near a famous Fe-Nb-REE deposit in northern China during the Early Paleozoic （or Mesoproterozoic as proposed by some researches）, while the latter indicates NE-SW-trending contemporaneous compression activities related to earthquakes in the Middle Triassic in the Nanpanjiang remnant basin covering south Guizhou, northwestern Guangxi and eastern Yunnan in southwestern China. The syn-sedimentary boudinage structure was found in an earthquake slump block in the lower part of the Early Paleozoic Sailinhudong Group, 20 km to the southeast of Bayan Obo, Inner Mongolia, north of China. The slump block is composed of two kinds of very thin layers-pale-gray micrite （microcrystalline limestone） of 1-2 cm thick interbedded with gray muddy micrite layers with the similar thickness. Almost every thin muddy micrite layer was cut into imbricate blocks or boudins by abundant tiny contemporaneous faults, while the interbedded micrite remain in continuity. Boudins form as a response to layer-parallel extension （and/or layer-perpendicular flattening） of stiff layers enveloped top and bottom by mechanically soft layers. In this case, the imbricate blocks cut by the tiny contemporaneous faults are the result of abrupt horizontal extension of the crust in the SE-NW direction accompanied with earthquakes. Thus, the rock block is, in fact, a kind of seismites. The syn-sedimentary boudins indicate that there was at least a strong earthquake belt on the southeast side of the basin during the early stage of the Sailinhudong Group. This may be a good constraint on the tectonic evolution of the Bayan Obo area during the Early Paleozoic time. The syn-sedimentary compression structure was found in the Middle Triassic flysch in the Nanpanjiang Basin. The typical structures are compression sand pillows and compression wrinkles. Both of them were found on the bottoms of sand units and the top surface of the underlying mud units. In other words, the structures were found only in the interfaces between the graded sand layer and the underlying mud layer of the flysch. A deformation experiment with dough was conducted, showing that the tectonic deformation must have been instantaneous one accompanied by earthquakes. The compression sand pillows or wrinkles showed uniform directions along the bottoms of the sand layer in the flysch, revealing contemporaneous horizontal compression during the time between deposition and diagenesis of the related beds. The Nanpanjiang Basin was affected, in general, with SSW-NNE compression during the Middle Triassic, according to the syn-sedimentary compression structure. The two kinds of syn-sedimentary tectonic deformation also indicate that the related basins belong to a rift basin and a remnant basin, respectively, in the model of Wilson Cycle.

Triassic Collisional Structures and Post-CollisionalDeformation of Bixiling UHP Rock Stack: Insightsfor Tectonic Evolution of UHP MetamorphicBelt in Dabie Massif, Central China

Detailed three-dimensional structural studies indicate that the Bixiling area, Dabie massif, central China shows the deepest exposed levels of the orogenic wedge formed during the Triassic Yangtze -Sino-Korean continental collision. New 1 : 10 000 scale structural mapping, combined with detailed petrological analysis in this area, has enabled us to accurately distinguish structures related to the Triassic continental collision from those related to post-collisional deformation in the ultrahigh pressure (UHP) metamorphic unit. The collisional or compressional structures include the massive eclogite with a weak foliation, foliated eclogite or UHP ductile shear zones, as well as upper amphibolite facies shear zones, whereas the post-collisional deformation is characterized by a regionally, flat-lying foliation containing stretching lineations and common reclined folds. The former is present exclusively in the eclogite lenses and their margins, representing orogenic thickening or syn-collisional events, while the latter was best occurred on variable scales under amphibolite facies conditions, showing sub-vertical, extreme shortening and ductile thinning of the metamorphic rock stack. The eclogite facies tectonites that have a marked fabric discordance to the penetrative amphibolite facies extension flow fabric are common. It is emphasized that an extensional tectonic setting following the collision-orogenic thickening stage was, at least partly, responsible for exhumation of the UHP metamorphic rocks in the Dabie massif. A new tectonic evolution model is proposed for the UHP metamorphic belt on the scale of the Dabie massif. The Bixiling area thus provides a window, from which the dynamic processes concerning the formation and exhumation of the UHP rocks can be observed. Regional studies in the Dabie Mountains have confirmed this interpretation.

Tectonic evolution of structures in Southern Sindh Monocline,Indus Basin,Pakistan formed in multi-extensional tectonic episodes of Indian Plate

There are a number of structures and structural styles found in extensional tectonic settings of the world,and it is a big challenge to study the evolution of these structures. Evolution of structures formed in extensional tectonic settings have been studied by researchers on different extensional basins of the world. Southern Sindh Monocline lies on the western corner of Indian Plate and the tectonic history of Indian plate has also experienced different extensional episodes, and its journey rifted from Gondwanaland to its final welding to Asia. The aim of this study is to figure out the evolution of structures in the subsurface of Southern Sindh Monocline, Pakistan using the seismic data interpretation and flattening of horizons approach. Structures within the subsurface of Southern Sindh Monocline have been characterized by different tectonic episodes of Indian plate while rifting from Gondwanaland, rifting from other plates at different geological times and to its collision with the Asia. Basic structures within study area are classified into nine types while the structural styles have been classified into six types as horst and grabens, dominos, crotch, synthetic and antithetic, negative and flashlight structural style. The structures within the study area revealed evidence for three major structural episodes which can be characterized as Episode 1: Structures associated with rifting of Indian plate from Gondwanaland during Late Jurassic to Early Cretaceous, Episode 2: Modification and reactivation of previous structures while Madagascar rifted from Indian Plate during the Middle Cretaceous and during Episode 3: Inversion and reactivation of structures occurred when Indian Plate collided with Asia during Early Eocene.

Cenozoic Tectonic Evolution of the Arcuate Structures in the Northeast Tibetan Plateau

The northeast Tibetan plateau contains important inlbrmation on the northeastward growth of the Tibetan plateau. It is bounded by the Ordos Block to the east, the Alxa Block to the north, and the Tibetan Plateau to the south （inset in Fig. 1; Tapponnier et al., 2001）, and has undergone complex intracontinental deformation during the Cenozoic. In this region, the northeast-convex arcuate structures developed northeastward, and are composed of a series of Cenozoic NW-SE-trending basin-and-range terrain, i.e., the Haiyuan-Xingrenbu basin, Tongxin basin and Hongsipu basin, the Yueliang Shan-Nanhua Shan- Huangjiawa Shan, Xiang Shan-Xiangjing Shan, Yantong Shan and Luo Shan-Niushou Shah, which is geometrically similar with the American basin-range tectonics.

Structural transformation of metal–organic framework with constructed tetravalent nickel sites for efficient water oxidation

A mixture of Ni and Fe oxides is among the most commonly active catalysts for the oxygen evolution reaction(OER)during the water oxidation process.In particular,Ni oxide incorporated with even a small amount of Fe leads to substantively enhanced OER activity.However,the critical role of Fe species during the electrocatalytic process is still under evaluation.Herein,we report nickel(oxy)hydroxide incorporated with Fe through the surface reconstruction of a bimetallic metal-organic framework(NiFe-MOF)during the water oxidation process.The spectroscopic investigations with theoretical calculations reveal the critical role of Fe in promoting the formation of highly oxidized Ni^(4+),which directly correlates with an enhanced OER activity.Both the geometric and electronic structu res of the as-reconstructed Ni_(1-x)Fe_(x)OOH electrocatalysts can be delicately tuned by the Ni-Fe ratio of the bimetallic NiFe-MOF,further affecting the catalytic activity.As a result,the Ni_(1-x)Fe_(x)OOH derived from Ni_(0.9)Fe_(0.1)-MOF delivers low overpotentials of 260 mV at 10 mA cm^(-2)and 400 mV at 300 mA cm^(-2).

Early-middle Mesoproterozoic tectonic evolutionary history of the southwestern Yangtze Block,China:lithostratigraphic,geochronologic and elemental geochemical constraints

During the Early-Middle Proterozoic era,three major lithostratigraphic unit associations,namely Hekou-Dahongshan,Dongchuan,and Kunyang-Huili Groups,were established for the metamorphosed volcanicsedimentary rocks exposed in the southwestern Yangtze Block (SWYB).The integration of petrology, geochemistry and geochronology constrains tectonic framework and evolution of the SWYB,in which four sets of SHRIMP U-Pb zircon ages were obtained from the volcanic rocks interbedded within the Middle Proterozoic successions:1800-1600 Ma,1600-1300 Ma,1300-1100 Ma,and 1100-1000 Ma. Major and trace elemental analysis indicate that four key tectonic evolutionary stages,each coinciding with the above radiometric age set,of the SWYB during the Early-Middle Mesoproterozoic.The SWYB was characterized by an east-westerly trending rift in the Hekou,Dongshan,and Dongchuan areas,and separate basin-forming events during 1800-1600 Ma arid 1600-1300 Ma,respectively.In the SWYB,an intracontinental rift basin and a rift basin occurred in the Caiziyuan-Matang and Laowushan areas, respectively in 1300-1100 Ma ago.During 1100-1000 Ma,the SWYB was characterized by the closure of the Caiziyuan-Matang rift-ocean basin,collision between the Huili Blocks and Kunyang Blocks,and presence of volcanic ares in the Tianbaoshan and Fulingpen areas.Accordingly,the SWYB represents a new basin that records the relatively complete assembly process of the Rodina during the Early-Middle Mesoproterozoic era.

The characteristics of geophysical field and tectonic evolutionin the Bransfield Strait

Having analysised the data collected by our survey ship'Ocean IV 'in the Bransfield Strait in 1991,we recognized that the geomorphology,gravity and magnetic anomalies trending NE direction along bandings. The sediments in the Bransfield Strait can be subdivided into two sequences:the first rifting equence and the second rifting sequence.The basement was faulted into a half-graben in northwestern side of the Bransfield trough. Considering the crustal structure crossing the South Shetland Islands,the Bransfield Strait and the Antarctic Peninsula, we propse a two-phase rifting tectonic evolution model and a layered-shear model for the lithospheric deformation under the effects of extensional stress field.

Multistage tectono-stratigraphic evolution of the Canavese Intracontinental Suture Zone:New constraints on the tectonics of the Inner Western Alps

The Canavese Intracontinental Suture Zone(CISZ) within the Inner Western Alps represents the remnant of a long-lived minor subduction zone involving a narrow, thinned continental crust/oceanic lithosphere seaway between two continental domains of the Adria microplate(i.e., the Sesia Zone and the IvreaVerbano Zone). As opposed to many suture zones, the CISZ mostly escaped pervasive tectonic deformation and metamorphism, thus preserving the original stratigraphy and allowing the relationships between tectonics and sedimentation to be defined. Through detailed geological mapping(1:5000 scale),structural analysis, stratigraphic and petrographic observations, we document evidences for the late Paleozoic to late Cenozoic tectonic evolution of the CISZ, showing that it played a significant role in the context of the tectonic evolution of the Inner Western Alps region from the early to late Permian Pangea segmentation, to the Jurassic Tethyan rifting, and up to the subduction and collisional stages,forming the Western Alps. The site of localization/formation of the CISZ was not accidental but associated with the re-use of structures inherited from regional-scale wrench tectonics related to the segmentation of Pangea, and from the subsequent extensional tectonics related to the Mesozoic rifting, as documented by crosscutting relationships between stratigraphic unconformities and tectonic features. Our findings document that evidences derived from stratigraphy, facies indicators, and relationships between tectonics and sedimentation in the shallow crustal portions of suture zones, such in the CISZ, are important to better constrain the tectonic history of those metamorphic orogenic belts around the world in which evolutionary details are commonly complicated by high-strain deformation and metamorphic transformations.

冀中坳陷南部中—新生代构造转换及其油气地质意义

为了分析冀中坳陷南部中—新生代构造转换机制及其与油气分布的关系,基于地震解释资料,对该区地质结构特征、构造演化及构造转换过程进行研究,并对其油气地质意义进行了探讨。结果表明:冀中坳陷南部衡水调节带两侧地质结构存在明显差异,北部为“双断-双向滑脱-背倾半地堑”结构,南部为“多断-单向滑脱-复式半地堑”结构;冀中坳陷南部地区中—新生代构造演化大致分为基底演化(中生代)、初始裂陷演化(孔店组—沙四段沉积时期)、强裂陷演化(沙三段—沙二段沉积时期)、弱裂陷演化(沙一段—东营组沉积时期)及后裂陷演化(馆陶组沉积时期以来)5个阶段;冀中坳陷南部经历了基底NNE向构造体系向新生代NE向构造体系的转换,区域中—新生代以来应力场变化是冀中坳陷多方位复杂构造形成的原因;冀中坳陷南部构造转换作用通过影响洼槽迁移进而影响有效烃源岩分布,通过控制砂体入盆通道影响储层砂体展布,构造变换过程中主干断层位移梯度变化导致横向背斜形成指示油气富集的有利部位。构造体制转换形成的不同规模变换构造具有一定勘探潜力。

阿尔金山冰沟一带花岗岩地球化学特征及对大地构造的演化启示

本文对出露于阿尔金山冰沟构造岩浆岩带内冰沟序列花岗岩进行了岩石学、地球化学、和锆石SHRIMP UPb年代学研究。地球化学特征显示:花岗岩高硅、钠,低铁、镁、钙的特征,铝饱和指数为0.88~1.01,为准铝质“I”型花岗岩;富集Rb,Th和LREE,亏损Ta,Nb,Zr,Hf和HREE;大多具负铕异常,δEu值为0.52~0.62。锆石U-Pb定年结果显示:冰沟序列侵入岩中花岗闪长岩年龄为(410.7±11.9)Ma,二长花岗岩年龄为(418.5±9.6)Ma,辉长岩年龄为(449.5±10.9)Ma。结合区域地质、地球化学特征揭示花岗岩岩体形成于后碰撞伸展阶段,认为同碰撞挤压造山阶段向后碰撞伸展转换阶段时间节点约为440 Ma,后碰撞伸展作用和偏碱性岩浆活动时代为440~410 Ma,持续约30 Ma。晚奥陶世北阿尔金古洋盆闭合,在有限洋盆造山带(冰沟序列侵入岩)形成规模较大的消减活动板块边缘(岛弧或活动大陆边缘)构造岩浆岩带。

新疆准噶尔盆地西北缘克拉玛依-乌尔禾断裂带推覆体上盘构造样式及影响因素

准噶尔盆地西北缘克拉玛依-乌尔禾断裂带(克-乌断裂带)及其周缘发现了大量的油气藏,尤其是推覆体上盘伴随着勘探程度及地质认识不断深化,已呈现出“百里油区”的态势。然而,受多期构造活动及断裂带内部复杂的岩性组合影响,石炭系内幕地层构造样式展现出多种类型及复杂的空间展布样式,因此需要对构造样式及成因进一步探讨。综合地震和钻井资料,结合区域构造格局,梳理了准噶尔盆地西北缘克-乌断裂带上盘构造变形特征与影响因素;根据构造样式与推覆体内的岩性组合类型,将克-乌断裂带推覆体上盘划分出南段、中段和北段3个变形单元;明确了上盘石炭系5期主要构造阶段,分段恢复了推覆体上盘构造演化期次及样式。综合上述研究,认为克-乌断裂带上、下盘原始岩性组合关系是造成上盘石炭系内幕地层原始形变差异的主要因素,上盘石炭系内幕地层岩性组合差异是造成原生构造保存的主要因素。上述因素共同造成了圈闭条件沿克-乌断裂带自南向北变化。该研究为克-乌断裂带上盘油气勘探提供指导,同时也为类似条件地区的油气勘探提供借鉴。

新疆库车坳陷东部中—新生代构造-热演化与油气勘探远景分析

【研究目的】库车坳陷油气资源丰富,但与油气生成与保存相关的构造-热演化研究很薄弱。【研究方法】本研究通过对库车坳陷东部典型钻孔样品开展磷灰石裂变径迹测试分析与热史模拟,精确重建了库车坳陷东部自中生代以来的构造-热演化史,并评价了烃源岩成熟演化期次。【研究结果】本文基于原位LA-ICP-MS法测试的磷灰石裂变径迹年龄介于77.7~104.5 Ma,远小于地层年龄,有效地记录了晚白垩世的快速隆升事件。通过热史模拟揭示出库车坳陷东部地区自侏罗纪以来经历了早白垩世—晚始新世(120~40 Ma)和晚中新世至今(10~0 Ma)两期快速隆升事件,分别是由拉萨地块、印度板块与欧亚板块南缘碰撞的远程效应造成的。【研究结论】库车坳陷东部地区的差异性构造隆升是由南天山由北向南逐渐推进的俯冲挤压造成的。库车坳陷东部地区侏罗系烃源岩在多期沉降作用影响下表现为多阶段成熟演化模式,但受构造隆升事件的影响,曾在早白垩世—晚始新世和晚中新世至今处于停滞阶段。本研究厘定了库车坳陷东部自中生代以来的构造-热演化史,明确了主要烃源岩成熟演化过程,对区域构造演化和下一步油气勘探具有重要的指导意义。

噻吩基二维共价有机框架中的拓扑结构诱导局部电荷极化促进光催化制氢

共价有机框架(COFs)是近年来新兴的一类多孔聚合物,在气体吸附、传感器、能源转换和光/电催化等领域表现出较大的应用潜力.然而,欲实现多样化的应用需求常需要对其结构进行合成后改性,这在单一步骤中难以实现.二维亚化学计量共价有机框架(2D-SSCOFs)因其独特的周期性官能团和保持结晶性及孔隙率的能力,成为COFs功能化的新途径.然而,已报道的2D-SSCOFs多具有相同的拓扑结构以及弱电荷极化等问题,限制了其应用潜力.因此,开发具有新颖拓扑结构的2D-SSCOFs对于实现更前沿的功能至关重要.窄带隙噻吩是有机半导体材料的常见单元,它们可以显著地调控共价聚合物骨架的电子和化学环境.本文通过5,5',5''-(苯-1,3,5-三基)三(噻吩-2-甲醛)(TT-3CHO)与4,4',4'',4''-(芘-1,3,6,8-四基)四苯胺(PY-4HN2)的席夫碱缩合反应合成具有大表面积和高结晶度的亚胺连接的新型2D-SSCOF(PTT-COF).噻吩环中2,5位之间的键的弯曲角度使得PTT-COF具有新型的2D亚化学计量拓扑结构,并呈现出非中心对称的优势极化结构.在使用有机空穴传输配体(二茂铁甲醛,FC)精确修饰和Pt作为助催化剂时,PTT-COF-FC体系在可见光照明下表现出较高的析氢产率(79.610 mmol g^(-1) h^(-1)).同时,在420 nm波长的光照下,2 mg的光催化剂表观量子效率达到1.72%.此外,经过24 h循环稳定性测试,PTT-COF-FC体系的活性没有明显下降.为了深入研究PTT-COF-FC体系的高效的产氢机制,通过X射线衍射、红外和固体碳谱等对PTT-COF-FC体系的组成和结构进行分析,确定了PTT-COF-FC的成功合成.通过瞬态吸收、变温荧光和理论计算等研究了材料的激子解离和载流子转移行为.结果表明,得益于独特的富含噻吩的结构设计以及有机空穴传输配体的修饰作用,PTT-COF-FC展现出高效的激子解离和丰富的自由电荷载流子特性.综上所述,本文设计和合成了一种新型PTT-COF光催化材料,其独特的二维亚化学计量拓扑结构和显著的局部电荷极化特性赋予了材料良好的光催化性能.实验和理论研究表明,PTT-COF中的非中心对称拓扑结构和噻吩单元的引入,有效扩展了π离域,进而诱导了局部极化并抑制了激子效应,从而大幅提高了光催化效率.此外,通过二茂铁甲醛的后修饰,结合这些独特的结构特性,PTT-COF在光催化析氢反应中表现出高活性和出色的长期耐久性.本文的研究不仅为设计和构建具有独特结构的新型2D-SSCOF提供新思路,也为构建具有丰富光催化功能的材料开辟了新途径.

辽河坳陷陈家断裂带北部构造演化解析及油气成藏

辽河坳陷陈家断裂带油气资源丰富,是辽河西部凹陷北段重要的含油气区带之一。基于构造演化解析,结合砂箱物理模拟实验,分析了辽河坳陷陈家断裂带的变形机制和演化过程,并指出其对油气成藏的控制作用。研究结果表明:(1)辽河坳陷陈家断裂带具有分段发育特征,且活动时期具有“先北后南”的演化特征,受断层分段性影响,陈家断裂带主要发育压扭背冲构造样式和走滑压扭构造样式。(2)物理模拟实验结果显示,台安—大洼断裂上盘在压扭作用影响下首先形成压扭性质的雁行小断裂,随着位移增大,小断裂逐渐连接,最终形成了贯穿型走滑断裂带,即陈家断裂带。(3)台安洼陷为新生代多期次构造变形叠加形成的洼陷,深层发育主力烃源岩层系,具备发育大规模油气藏的物质基础,洼陷边缘的钻井岩心分析结果显示,烃源岩TOC值为4.79%,Ro为0.3%~0.4%,属于好—较好烃源岩,推测洼陷中心厚度更大,质量更优。陈家断裂带中北部下盘发育断鼻构造,具备陈家洼陷和台安洼陷双源供烃的特点,是油气聚集的有利场所。

有机框架结构对NiFe-MOF析氧反应的影响

合理设计用于电解水制氢阳极析氧反应(OER)的高活性电催化剂对清洁能源和生态可持续发展至关重要。然而,由于OER四电子转移的动力学过程较为缓慢,导致过电位较高,开发高效的阳极催化剂仍是一个重大挑战。金属有机框架(MOF)因结构多样性和超高的比表面积被视为有潜力的OER电催化剂。NiFe双金属材料具有优异的阳极析氧催化活性,但针对MOF材料活性的调控主要集中在金属中心的设计上,而阴离子有机配体对阳极析氧催化活性的影响依然未知。因此,采用溶剂热法构建具有等网状结构的系列羧酸型NiFe-MOF来阐明羧酸连接体不同长度对OER性能的影响(三种不同的有机配体分别为:对苯二甲酸(BDC)、2,6-萘二甲酸(NDC)和4,4′-联苯二甲酸(BPDC))。通过X射线衍射、拉曼光谱、红外光谱、扫描电子显微镜和X射线光电子能谱,分析了催化剂的性质、微观形貌和电荷结构,并在1 mol/L KOH溶液中进行了电化学测试。结果表明:NiFe-BDC在10 mA/cm^(2)的电流密度处过电位仅为223 mV,远低于NiFe-NDC和NiFe-BPDC的过电位,二者此处的过电位分别为267 mV和284 mV;此外,NiFe-BDC在长时间测试中表现了出色的稳定性(200 h),其优异的性能主要归因于有机配体在催化中起到优化电荷结构的作用,并且展现出丰富的活性中心,共同促进了OER电催化性能。

湘南大义山地区中—新生代变形序列及其动力学背景

大义山地区处于南岭构造带与钦杭构造带结合部位,自早中生代以来发育多方向、不同类型的构造,这些变形的先后序次对理解湘南及邻区的构造演化过程具有基础性意义,然而目前其构造变形特征和应力场演替过程仍缺乏精细剖析。本文运用构造解析方法对大义山地区地表基岩中的剪切破裂和褶皱等构造要素进行分期和配套,利用赤平投影法恢复剪切破裂的古构造应力场,结合中—新生代华南大地构造演化历史,厘定了研究区5期构造变形事件及其动力学背景:第1期NEE—SWW向挤压(D_(1))发生于中三叠世晚期印支运动早幕,其动力学背景可能为多板块围限下的扬子克拉通与华夏地块间继发性陆内俯冲汇聚,而局部与区域挤压方向的差异性,可能与NW向邵阳—郴州断裂左行走滑派生的近E—W向挤压应力场及走滑所产生的逆时针牵引作用有关;第2期近S—N向挤压(D_(2))形成于晚三叠世—早侏罗世印支运动晚幕,可能与华北克拉通向南的挤压和思茅—印支地块向北的挤压有关;第3期NWW—SEE向挤压(D_(3))为中侏罗世晚期早燕山运动的产物,其动力来源于古太平洋板块(或伊泽奈崎板块)对华南大陆的西向俯冲;第4期与岩浆作用相关变形(D_(4))包括褶皱、挤压面理、肿缩构造和张剪性破裂等,可能受制于早燕山运动后造山阶段晚侏罗世花岗质岩浆沿不同方向基底断裂的幕式上侵和侧向流动;第5期N(N)E—S(S)W向挤压(D_(5))发生于古近纪中晚期,可能与先存NNE向断裂带右行走滑所派生的局部挤压应力场有关,其动力学机制可能为印度板块与欧亚板块碰撞而引发的青藏高原物质东向逃逸。进一步分析认为,NW向邵阳—郴州断裂最强烈的走滑活动可能发生在印支运动早幕,并由此奠定了断裂周缘中—新生代构造格架。