Reconstructed Water Oxidation Electrocatalysts: The Impact of Surface Dynamics on Intrinsic Activities

Electroreduction of small molecules such as H₂O, CO₂, and N₂ for producing clean fuels or valuable chemicals provides a sustainable approach to meet the increasing global energy demands and to alleviate the concern on climate change resulting from fossil fuel consumption. On the path to implement this purpose, however, several scientific hurdles remain, one of which is the low energy efficiency due to the sluggish kinetics of the paired oxygen evolution reaction (OER). In response, it is highly desirable to synthesize high-performance and cost-effective OER electrocatalysts. Recent advances have witnessed surface reconstruction engineering as a salient tool to significantly improve the catalytic performance of OER electrocatalysts. In this review, recent progress on the reconstructed OER electrocatalysts and future opportunities are discussed. A brief introduction of the fundamentals of OER and the experimental approaches for generating and characterizing the reconstructed active sites in OER nanocatalysts are given first, followed by an expanded discussion of recent advances on the reconstructed OER electrocatalysts with improved activities, with a particular emphasis on understanding the correlation between surface dynamics and activities. Finally, a prospect for clean future energy communities harnessing surface reconstruction-promoted electrochemical water oxidation will be provided.     

Substrate temperature-controlled precursor reaction mechanism of PEALD-deposited MoOx thin films

Journal of Materials Science - Molybdenum oxide (MoOx) films had been grown by using plasma-enhanced atomic layer deposition (PEALD) with Mo(CO)6 precursor and O2 plasma reactant in a substrate...     

Advances in statistical mechanics of rock masses and its engineering applications

To efficiently link the continuum mechanics for rocks with the structural statistics of rock masses,a theoretical and methodological system called the statistical mechanics of rock masses(SMRM)was developed in the past three decades.In SMRM,equivalent continuum models of stressestrain relationship,strength and failure probability for jointed rock masses were established,which were based on the geometric probability models characterising the rock mass structure.This follows the statistical physics,the continuum mechanics,the fracture mechanics and the weakest link hypothesis.A general constitutive model and complete stressestrain models under compressive and shear conditions were also developed as the derivatives of the SMRM theory.An SMRM calculation system was then developed to provide fast and precise solutions for parameter estimations of rock masses,such as full-direction rock quality designation(RQD),elastic modulus,Coulomb compressive strength,rock mass quality rating,and Poisson’s ratio and shear strength.The constitutive equations involved in SMRM were integrated into a FLAC3D based numerical module to apply for engineering rock masses.It is also capable of analysing the complete deformation of rock masses and active reinforcement of engineering rock masses.Examples of engineering applications of SMRM were presented,including a rock mass at QBT hydropower station in northwestern China,a dam slope of Zongo II hydropower station in D.R.Congo,an open-pit mine in Dexing,China,an underground powerhouse of Jinping I hydropower station in southwestern China,and a typical circular tunnel in Lanzhou-Chongqing railway,China.These applications verified the reliability of the SMRM and demonstrated its applicability to broad engineering issues associated with jointed rock masses.     

Evolution of Local Structural Ordering and Chemical Distribution upon Delithiation of a Rock Salt–Structured Li1.3Ta0.3Mn0.4O2 Cathode

Lithium‐rich disordered rock‐salt oxides have attracted great interest owing to their promising performance as Li‐ion battery cathodes. While experimental and theoretical efforts are critical in advancing this class of materials, a fundamental understanding of key property changes upon Li extraction is largely missing. In the present study, single‐crystal synthesis of a new disordered rock‐salt cathode material, Li_1.3Ta_0.3Mn_0.4O₂ (LTMO), and its use as a model compound to investigate Li concentration–driven evolution of local cationic ordering, charge compensation, and chemical distribution are reported. Through the combined use of 2D and 3D X‐ray nanotomography, it is shown that Li removal accompanied by oxygen oxidation is correlated with the development of morphological defects such as particle cracking. Chemical heterogeneity, quantified by subparticle level distribution of Mn valence state, is minimal during Mn redox, which drastically increases upon the formation of cracks during oxygen redox. Density functional theory and bond valence sum mismatch calculations reveal the presence of local short‐range ordering in the pristine oxide, which gradually disappears along with the extraction of Li. The study suggests that with cycling the transformation into true cation–disordered state can be expected, which likely impacts the voltage profile and obtainable energy density of the oxide cathodes.     

负载型Pt-Fe/SiO_2催化剂催化环己烷一步氧化制己二酸

己二酸是合成尼龙-66和尼龙-46纤维的重要原料,并进一步用于生产许多重要的化工产品。工业上的己二酸多采用以硝酸为氧化剂的两步法合成,该工艺不仅工艺复杂,而且对设备有腐蚀作用,还会释放大量的温室气体N_2O。本文以负载型Pt/SiO_2、Fe/SiO_2和Pt-Fe/SiO_2为催化剂,采用过氧化氢和氧气为氧源,研究了环己烷一步氧化制己二酸的绿色合成路线。对催化剂进行ICP、BET比表面积、XRD、TEM等表征,结果表明,Pt-Fe/SiO_2催化剂中不存在与Pt或Fe对应的衍射峰。在最佳反应条件下,用高压釜进行了催化剂性能评价,结果表明,Pt-Fe/SiO_2催化活性略优于Pt/SiO_2和Fe/SiO_2。在环己烷转化率为28%的情况下,己二酸选择性达到33%。     

Tribological and corrosion behaviors of fluorocarbon coating reinforced with sodium iron titanate platelets and whiskers

A series of sodium iron titanate (NFTO)–fluorocarbon composite coatings have been prepared with the liquid-phase blending method. The effects of two types of NFTO, NFTO platelets, and NFTO whiskers, on the tribological and corrosion behaviors of the composite coatings, are systematically studied. The results show that the addition of NFTO can significantly enhance the friction-reducing and wear resistance performances of the fluorocarbon coating. Under dry sliding, the minimum specific wear rate is 1.67 × 10⁻⁴ mm³/Nm for the platelet-filled composite coatings and 1.15 × 10⁻⁴ mm³/Nm for the whisker-filled composite coatings, respectively, showing a decrease of 83.5 and 88.6% than that of pure coating. Under a simulated seawater environment, the minimum specific wear rate is 5.44 × 10⁻⁵ mm³/Nm for the platelet-filled composite coatings and 0.84 × 10⁻⁵ mm³/Nm for the whisker-filled composite coatings, respectively, showing a decrease of 90.5 and 98.5% than that of pure coating. The morphologies of worn surfaces, wear debris, and transfer films are analyzed, and the corresponding wear resistance mechanisms are discussed. The electrochemical impedance spectroscopy certifies a remarkably improved corrosion resistance of the composite coatings which have been immersed in 3.5 wt % NaCl solution for 30 days. The composite coating reinforced with 7.5 wt % platelets shows the highest resistance of 256.3 × 10⁶ Ω·cm², approximately two orders of magnitude higher than that of pure coating. © 2020 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2020 , 137, 48936.     

CO2驱沥青质沉积对致密储层的伤害机理——以鄂尔多斯盆地延长组长8储层为例

为了揭示CO2驱替过程中沥青质沉积对致密储层的伤害机理,文中基于岩心核磁共振T2谱测试原理,开展了CO2注入压力下的岩心驱替实验,研究了沥青质在岩心中的沉积特征,评价了沥青质沉积对储层的伤害程度。实验结果表明:沥青质沉积量和渗透率伤害率随着CO2注入压力的升高呈现先快速上升后趋于平缓的趋势;在CO2注入过程中,沥青质主要沉积在弛豫时间大于10 ms的大、中孔隙,导致大、中孔隙占比下降,微细、小孔隙占比增加,且随着CO2注入压力的升高,大、中孔隙占比下降幅度增大,微细、小孔隙占比上升幅度增大;此外,沥青质沉积会引起润湿性发生反转,随着沥青质沉积量的增加,润湿反转指数增大,岩心润湿性不断向强油湿方向转变。     

45号钢垫圈断裂的原因分析和改进措施

针对45号钢垫圈在装配后发生断裂的情况,对45号钢垫圈进行断口形貌分析、力学性能分析、化学成分分析和金相组织分析。宏观形貌显示内孔存在加工台阶和明显刀痕,能谱测试发现断裂起始处存在锌元素,金相组织分析确认内孔加工面存在微裂纹。结合加工工艺分析,确认45号钢垫圈的断裂原因,并提出改进措施。     

高温烟气中煤焦气化行为

针对高温烟气中煤焦的气化行为，本文采用FactSage 6.1计算了煤焦在高温烟气下的高温反应特性，并利用热重分析仪分析了煤焦气化行为。通过沉降炉实验进一步研究了不同温度、气体配比、粒径条件下气体产物的动态析出特性，同时计算了评价指标α、β、LHV值。结果表明：随着温度的升高，气体产物H₂和CO的含量增加，β、α、LHV值增大，CH₄和CO₂的含量下降。在温度为1200℃时，β、α值分别由CO₂/CO比为10∶70时的10.80%、5.21%增加到CO₂/CO比为50∶30时的24.71%、41.06%。同时，随着CO₂/CO比值的增大，高温烟气对煤焦气化反应抑制减弱。通过对比反应温度和粒径对煤焦气化反应的影响，得出反应温度远大于粒径对煤焦气化反应的影响。通过实验验证了向高温烟气中喷吹煤焦制备高品质可燃气体方法的可行性。