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.     

致密砂岩油藏能量补充方式评价及优化

针对致密砂岩油藏大规模体积压裂开发后能量补充困难的问题,利用自主设计制作的大型人造三维岩心物理模型和物理模拟实验舱,开展致密砂岩油藏能量补充方式优化研究。实验结果表明:致密砂岩油藏压裂开发过程中,地层能量损耗严重,采取注水或注气的方式可有效进行能量补充;地层中裂缝规模越大,越有利于原油渗流,后续补充能量的传播范围越广,有助于进一步提高原油采收率;从提高驱油效率和扩大波及系数方面优选吞吐渗吸介质,CO₂均优于活性水,CO₂吞吐开发在矿场试验中取得了显著的增油效果,因此,CO₂吞吐作为一种有效的能量补充方式在致密油开发中展现了良好的应用前景。该文分析了致密砂岩储层水平井压裂开发的渗流规律,优选出致密砂岩储层大规模压裂开发后最佳渗吸介质,可为致密砂岩油藏开发设计提供重要的理论依据。     

Electronic regulation and core-shell hybrids engineering of palm-leaf-like NiFe/Co(PO3)2 bifunctional electrocatalyst for efficient overall water splitting

Constructing efficient and stable bifunctional electrocatalysts for overall water splitting remains a challenge because of the sluggish reaction kinetics. Herein, the core-shell hybrids composed of Co(PO₃)₂ nanorod core and NiFe alloy shell in situ grown on nickel foam (NiFe/Co(PO₃)₂@NF) are synthesized. Owing to the hierarchical palm-leaf-like structures and strong adhesion between NiFe alloys, Co(PO₃)₂ and substrates, the catalyst provides a large surface area and rapid charge transfer, which facilitates active sites exposure and conductivity enhancement. The interfacial effect in the NiFe/Co(PO₃)₂ core-shell structure modulates the electronic structure of the active sites around the boundary, thereby boosting the intrinsic activity. Benefiting from the stable structure, the durability of the catalyst is not impaired by the inevitable surface reconfiguration. The NiFe/Co(PO₃)₂@NF electrode presents a low cell voltage of 1.63 V to achieve 10 mA cm^?2 and manifests durability for up to 36 h at different current densities.     

Enhanced hydrogen production from water splitting by Sn-doped ZnO/BiOCl photocatalysts and Eosin Y sensitization

The construction of semiconductor heterojunction for photocatalytic H₂ production from water splitting is an efficient and environment-friendly technology. In this work, ZnO/BiOCl (ZBC) and Sn-doped ZnO/BiOCl (ZBC-S) photocatalysts with Z-scheme heterojunction were successfully prepared by simple hydrothermal method. The photocatalytic H₂ evolution from water splitting by the as-prepared photocatalysts was investigated. The formation of ZnO/BiOCl heterojunction reduces the recombination probability of the photogenerated carriers. The impurity levels originated from Sn doping reduce the band gap width of ZnO and BiOCl to some extent, thereby enhancing the light absorption ability. The ZBC-S composite exhibits the best photocatalytic activity. In addition, the photocatalytic efficiency of H₂ production was improved by sensitization with Eosin Y (EY) dye. The H₂ production rate under simulated sunlight reaches 4146.77 μmol g^?1 h^?1, which is 27 times higher than that of pure ZnO. Finally, the Z-scheme electron transfer route in ZnO/BiOCl heterojunction was determined, and the photocatalytic H₂ production mechanism of EY sensitized ZBC-S was proposed.     

Layered double (Ni,Fe) hydroxide grown on nickel foam and modified by nickel carbonyl powder and carbon black as an efficient electrode for water splitting

Developing novel oxygen evolution reaction (OER) and hydrogen evolution reaction (HER) catalysts is vital for water splitting. Here, carbon black (CB) and nickel carbonyl powder (NCP) are used as components, and the nonionic surfactant polyvinyl pyrrolidone (PVP) is used as a shape-controlled capping agent to easily prepare layered double (Ni, Fe) hydroxide (NiFe-LDH) electrodes. Scanning electron microscopy observation and X-ray photoelectron spectra analysis show that the Fe²⁺-doped layered double hydroxide is grown in situ on nickel foam (NF). CB (XC-72) and NCP further improve the electrical conductivity. At 10 mA?cm^?2, the overpotentials of the OER and HER are 203 mV and 83 mV, respectively, in 1 M KOH. Only 1.48 V is needed when both electrodes are applied for water splitting, and it has a stability of more than 100 h. This work can be used as a medium to elevate the OER and HER performance of NiFe-LDH-based catalysts.     

Kinetic Monte Carlo simulation of hydrogen production from photocatalytic water splitting in the presence of methanol by 1 wt% Au/TiO2

In this research, using the kinetic Monte Carlo simulation (KMC), the hydrogen production from a water-methanol mixture using Au/TiO₂ photocatalyst is investigated. A mechanism is proposed, and the rate constants of the reaction steps are specified. The reaction rate constants of different steps and the concentration of the active sites on the photocatalyst surface were determined. An excellent match between simulated and experimental data confirms the results. The electron-hole pair production, methanol adsorption on the photocatalyst surface, and electron-hole recombination steps are considered the most critical steps. To study the effects of independent variables (initial concentration of methanol, photocatalyst dosage, pH, and time of reaction) on the produced hydrogen, a combination of KMC simulation and design of experiment was employed. The concentration of photocatalysis has the highest and pH has the lowest effect on the hydrogen production. The optimal conditions for photocatalytic hydrogen production are presented.     

基于ERNIE-BiGRU模型的摘要语步自动识别研究

学术文献的摘要是对文献主要内容的浓缩,摘要不同部分的语步具有不同的信息,语步的自动识别和抽取对于学术摘要的后续研究有着重要的应用价值,而目前语步识别的研究相对较少,并且相关算法的效果还需要提高。针对上述问题,该文提出了一种基于ERNIE-BiGRU模型的语步识别算法。该算法首先结合中文句法分析理论提出基于句法依存关系的多语步结构拆分法,对学术文献摘要多语步结构进行自动拆分,获得多个单语步结构;然后构建用于训练的单语步结构语料库,并利用知识增强语义表示预训练模型,训练出句子级词向量;最后将训练出的单语步结构词向量信息输入双向门限循环单元(BiGRU)进行摘要语步自动化识别,取得了良好的效果。实验结果表明,该算法具有较好的鲁棒性和较高的识别精度,在结构化和非结构化摘要上的识别准确率分别达到了96.57%和93.75%。     

Ni2P(O)–Fe2P(O)/CeOx as high effective bifunctional catalyst for overall water splitting

The development of cost-effective bifunctional catalysts with excellent performance and good stability is of great significance for overall water splitting. In this work, NiFe layered double hydroxides (LDHs) nanosheets are prepared on nickel foam by hydrothermal method, and then Ni₂P(O)–Fe₂P(O)/CeO_x nanosheets are in situ synthesized by electrodeposition and phosphating on NiFe LDHs. The obtained self-supporting Ni₂P(O)–Fe₂P(O)/CeO_x exhibit excellent catalytic performances in alkaline solution due to more active sites and fast electron transport. When the current density is 10 mA cm^?2, the overpotential of hydrogen evolution reaction and oxygen evolution reaction are 75 mV and 268 mV, respectively. In addition, driven by two Ni₂P(O)–Fe₂P(O)/CeO_x electrodes, the alkaline battery can reach 1.45 V at 10 mA cm^?2.     

Simply constructed highly dispersed cobalt nanoparticles in diverse N-doped graphitic carbon with remarkable performances for water electrolysis

Metal/carbon composite materials are highly promising electrocatalysts for water electrolysis. In this work, three composites of metal cobalt nanoparticles highly dispersed in N-doped carbon materials were facilely constructed by pyrolysis of different phenylenediamine based Schiff base-Co complexes (PDBs). Interestingly, the composites derived from PDBs based on different phenylenediamine exhibited different morphologies. The superior case is that rodlike composite catalyst was derived from o-phenylenediamine based PDBs. The obtained catalyst exhibited remarkable performances for both cathodic hydrogen evolution reaction (HER) and anodic oxygen evolution reaction (OER), as well as overall water electrolysis. Only 172 and 289 mV of overpotentials and 1.57 V of cell voltage were exhibited at 10 mA cm^?2 for HER, OER and water splitting in 1.0 M KOH, respectively. The catalyst also displayed robust stability and high Faraday efficiency, and thus are potential high-performance catalyst for commercial water electrolysis.     

Synthesis of bristlegrass-like Co-doped Ni2P composites on Ni foam for overall seawater splitting

Seawater is the most abundant resource on earth, so developing cost-effective, highly durable corrosion resistance and efficient electrocatalysts are crucial to enhance seawater splitting. Herein, we prepared 3D bristlegrass-like Co-doped Ni₂P (Co-Ni₂P) composites supported on Ni foam (NF) through a facile solvothermal method combined and a subsequent phosphatization treatment. Benefiting from the unique structure, Co-Ni₂P shows excellent electrocatalytic activity as an electrode material for both the hydrogen evolution reaction (HER, low overpotential of 116 mV at 50 mA cm^?2) and oxygen evolution reaction (OER, low overpotential of 266 mV at 50 mA cm^?2). Moreover, the as-prepared Co-Ni₂P composites exhibit excellent stability and corrosion resistance in an alkaline medium. Density functional theory (DFT) calculations were employed to evaluate the H1 adsorption of Co-Ni₂P, and the results proved the high catalytic activity for the HER. This study provides new materials with a unique morphology for overall water splitting.