Re-Looking into the Active Moieties of Metal X-ides (X- = Phosph-, Sulf-, Nitr-, and Carb-) Toward Oxygen Evolution Reaction

Non-precious metal-based catalysts for oxygen evolution reaction (OER) have been extensively studied, among which the transition metal X-ides (including phosph-ides, sulf-ides, nitr-ides, and carb-ides) materials are emerging as promising candidates to replace the benchmark Ir/Ru-based materials in alkaline media. However, it is controversial whether the metal Xides host the real active sites since these metal Xides are thermodynamically unstable under a harsh OER environment—it has been reported that the initial metal Xides can be electrochemically oxidized and transformed into corresponding oxides and (oxy)hydroxides. Therefore, the metal Xides are argued as “pre-catalysts”; the electrochemically formed oxides and (oxy)hydroxides are believed as the real active moieties for OER. Herein, the recent advances in understanding the transformation behavior of metal Xides during OER are re-looked; importantly, hypotheses are provided to understand why the electrochemically formed oxides and (oxy)hydroxides catalysts derived from metal Xides are superior for OER to the as-prepared metal oxides and (oxy)hydroxides catalysts.     

Synergistic regulation of hydrogen adsorption/desorption via dual interfaces of Cu/Ni/Ni(OH)2 toward efficient hydrogen evolution reaction

Nickel-based catalysts have attracted tremendous attention as alternatives to precious metal-based catalysts for electrocatalytic hydrogen evolution reaction (HER) in virtue of their conspicuous advantages such as abundant reserves and high electrochemical activity. Nevertheless, a great challenge for Ni-based electrocatalyst is that nickel sites possess too strong adsorption for key intermediates H1, which severely suppresses the hydrogen-production activities. Herein, we report a hierarchical architecture Cu/Ni/Ni(OH)₂ consisting of dual interfaces as a high-efficient electrocatalyst for HER. The Cu nanowire backbone could provide geometric spaces for loading plenty of Ni sites and the formed Ni/Cu interface could effectively weakened the adsorption intensity of H1 intermediates on the catalyst surface. Moreover, the H1 adsorption could be further controlled to appropriate states by in-situ formed Ni(OH)₂/Ni interface, which simultaneously promotes water adsorption and activation, thus both Heyrovsky and Volmer steps in HER could be obviously accelerated. Experimental and theoretical results confirm that this interface structure can promote water dissociation and optimize H1 adsorption. Consequently, the Cu/Ni/Ni(OH)₂ electrocatalyst exhibits a low overpotential of 20 mV at 10 mA cm^?2 and an ultralow Tafel slope of 30 mV dec^?1 in 1.0 M KOH, surpassing those of reported transition-metal-based electrocatalysts and even the prevailing commercial Pt/C.     

油气田开发新技术的优化

为了满足石油企业在油气田开发中后期阶段也能达到生产需求,就需要采用油气田开发新技术,对油气田开发新技术进行研究,优化油气田现有开发工艺技术,不断提高油气田开发的效果,提高油气田剩余产能,为石油企业带来最大的经济效益。     

苏6区块气藏剩余储量评价及提高采收率对策

针对致密砂岩气藏剩余储量分布及提高采收率对策不明晰的问题,以苏6区块为例,通过气藏精细描述,明确了区块的有效砂体展布特征及气藏剩余储量分布类型,估算了各类型气藏剩余储量占比;基于气藏剩余储量分布特点,应用经济技术指标评价方法,确定了合理的直井井网密度,提出了通过直井井网加密来提高气藏采收率的技术对策。研究结果表明,苏6区块剩余储量分布类型主要为井网未控制型、水平井遗留型、直井遗留型,直井遗留型又可细分为射孔不完善型、复合砂体内部阻流带型2个亚类。其中,井网未控制型为主力剩余气,占总剩余储量的67.7%,为主要挖潜对象。合理的直井井网密度为4口/km2,加密后区块采收率可提高至48%左右。     

Influence of zinc and cadmium co-doping on optical and magnetic properties of cobalt ferrites

Zinc and cadmium based cobalt ferrites Zn_xCd_0.375-xCo_0.625Fe₂O₄ (where x = 0, 0.075, 0.125, 0.25) were successfully synthesized by a facile co-precipitation technique. Structural, optical and magnetic characteristics of the doped ferrites were systematically analyzed. X-ray Diffraction (XRD) pattern confirmed the formation of cubic spinel structure in all samples. Scanning electron microscopic analysis of surface morphology revealed cubic and spherical shaped ferrite particles. Fourier transform infrared (FTIR) spectroscopy confirmed the existence of metal oxygen (M − O) bonding in the prepared samples. Moreover, the prepared samples exhibited two frequency bands corresponding to phonon vibrational stretching in both octahedral and tetrahedral lattice positions. The optical properties were investigated in detail through photoluminescence (PL) spectroscopy and Raman spectroscopy. The PL spectrum confirmed the strong emission peaks in the ultraviolet to visible region of all the samples. Further, four active Raman modes, associated with cubic spinel structure are identified in all prepared samples. Finally, the magnetic characteristics are evaluated by using vibrating sample magnetometer (VSM) revealing ferrimagnetic and soft magnetic behavior of the samples. As the Zn and Cd co-doping in Co was increased, the H_c was decreased. The magnetic studies show the maximum H_c of 576 Oe for Cd doped cobalt ferrite, and maximum saturation magnetization (M_s) for Zn–Cd doped cobalt ferrite. It is envisaged that the newly prepared Zn–Cd co-doped cobalt ferrite would be appropriate for a number of important applications, for example, magnetic recording devices, sensors, actuators, high-density data storage devices, and biomedical equipments.     

主溜井排尘与生产分区并联回风技术研究

四川某矿山东部上部作业区域处于东、西部分区通风系统之外，针对原主通风系统无法负担此区域的实际情况，为节省新系统投资及建设周期，研究利用其1#主溜井排尘通风系统与此区域形成并联回风通路的方式解决该区域通风问题，即东部上部区域端部回风井污风与排尘风井污风并联回风汇至上部汇风中段，汇集污风统一经由上部排尘风机排至地表，该系统方案既保障了矿井东部上部作业中段（分段）生产用风与溜井排尘用风的需求，同时节约矿井东部上部系统独立建设及运行成本。     

红阳二矿12号煤层标志性气体实验研究

针对红阳二矿12号煤层遗煤氧化的规律与特点，有效地进行防灭火工作，掌握采空区中遗煤氧化的速度，对红阳二矿12号煤层进行了煤样升温氧化实验，在温度不断升高的过程中检测出CO与多种烯烃气体，并且在不同温度下煤体析出气体的速度不同，最终选择CO、C₂H₄、C₂H₂作为标志性气体，产生的临界温度分别为59、176、403 ℃。在采空区检测出CO气体，说明采空区遗煤进入快速氧化阶段；检测出C₂H₄气体时，遗煤进入剧烈氧化状态；检测出C₂H₂气体时，说明采空区中已经产生明火，井下人员需要迅速撤离。通过煤体标志性气体的确定，建立12号煤层自燃预警系统，保证井下工作人员的生命安全与能源的充分利用。     

Effect of Fe/Zn ratio in composite catalyst for synthesizing polyoxymethylene dimethyl ethers

Polyoxymethylene dimethyl ethers (PODE_n) are extremely effective diesel additives to reduce soot formation during combustion. We introduce a series of Fe-Zn composite solid acid catalysts (SO₄²⁻/xFe₂O₃-yZnO), for the condensation reaction of methanol and paraformaldehyde (PF) with a cheap and feasible route to efficiently synthesize PODE_n. These catalysts were characterized by different characterization techniques, namely BET, XRD, SEM, EDS, FTIR, and NH₃-TPD and the results showed that Fe/Zn molar ratios strongly influenced the physicochemical characteristics of catalysts, thus affecting the methanol conversion and PODE_1-6 and PODE_3-6 selectivity. Accordingly, the methanol conversion was decreased and the selectivity of PODE_3-6 was increased after increasing the Zn molar content. Comparatively, SO₄²⁻/Fe₂O₃-2ZnO exhibited superior catalytic activity among the various investigated catalysts due to the high acid density of strong acid sites. The optimal reaction conditions were observed to be at a 3.0 wt% catalyst loading (catalyst/reactant mass ratio), 2.5 hours ours of reaction time, a reaction temperature of 403 K, and a molar ratio of 3:1 of CH₂O to methanol, achieving a high selectivity of 99.09% PODE_1-6 and 28.23% PODE_3-6 with 55.16% methanol conversion during the reaction.     

Identification of active sites in CO2 activation on MgO supported Ni cluster

In this work, initial activation mechanism of CO₂ over MgO supported Ni catalysts has been systematically studied through the periodic DFT calculations. In addition, the role of metal cluster, interface and support for CO₂ activation is investigated and the active site is identified. CO₂ is most favored to be activated on the interface instead of neither Ni cluster nor MgO support. The effective energy for this process is around 0.67 eV, and the dissociation of CO₂ (0.62 eV) is the rate-determining step, since it requires much higher energy than that of the CO₂ adsorption process (0.05 eV). Thus, the interface between metal cluster and support plays a key role for C=O bond activation. Moreover, CO1 is preferred to be adsorbed on the Ni cluster, while the O1 is likely to bind on Mg atom of support. To illustrate the adsorption behavior of CO₂ at different sites, the Mulliken atomic charge and electron density difference have been calculated. It was found that the total amount of electron gain for CO₂ binding at different sites follows the order of Interface (−0.03 e) < MgO support (−0.05 e) < Ni cluster (−0.07 e), and effective energy barrier rises linearly with the increase of electron gain of CO₂ binding at different sites. In addition, electron gain of oxygen atom O1 and oxygen atom O2 of CO₂ is the same for Ni cluster and MgO support, however, the electron gain of O1 and O2 is different for Interface. The difference of electron gain for two oxygen atoms shows the electron unbalance of CO₂ molecule, which is in favor of C=O activation. This study could shed some light on understanding the active sites of CO₂ thermal-catalytic activation over MgO supported Ni catalysts, and is helpful to elucidate the reaction on an atomic level.