CNT/Fe-Ni/TiO_2/ZnO阵列修饰Ni阳极的制备及光催化制氢性能

采用层层自组装方法在Ni片阳极上构建TiO2/Zn O纳米棒阵列,以二氧化钛前驱体溶胶中掺杂的铁和镍为催化剂,通过气相沉积法在TiO2/Zn O纳米棒阵列间原位生长碳纳米管(CNTs),得到CNT/Fe-Ni/TiO2/Zn O复合光催化剂修饰的光活性Ni片阳极.以碱性电解池为基础,用紫外线辐照修饰的Ni阳极实现光催化和电解水的有机耦合制氢过程.通过场发射扫描电子显微镜(FESEM)、透射电子显微镜(TEM)、拉曼光谱(Raman)和电化学阻抗谱(EIS)对CNT/Fe-Ni/TiO2/Zn O复合膜光催化剂的结构进行了表征,并测试了其光催化辅助电解水制氢(WEAP)活性.结果表明,生长了碳纳米管的光催化复合膜CNT/Fe-Ni/TiO2/Zn O修饰的Ni阳极的产氢速率分别比Fe-Ni/TiO2/Zn O修饰的Ni阳极和纯Ni片提高了93.7%和533.0%.     

氧化钙对胜利褐煤焦水蒸气气化反应性能及微结构的影响

研究了CaO对胜利褐煤焦水蒸气气化反应性能及微结构的影响。脱除矿物质的胜利褐煤混合不同含量的CaO后在1 100 ℃下进行热解得到相应的煤焦,采用BET、XRD和Raman技术对其进行表征,同时在微型固定床反应器上对所制得煤焦进行水蒸气气化实验。比较添加CaO不同含量煤焦的反应性表明,添加2%(质量分数)的CaO对煤焦水蒸气气化的催化作用很小,而CaO添加量增大到5%时,煤焦的气化反应性能明显提高。煤焦比表面积随CaO添加量的提高而增大。XRD结果表明,在热解过程中,CaO能有效地抑制煤焦向石墨化方向发展趋势。煤焦002和100峰的峰强度随CaO添加量的增加而降低,且煤焦芳香度从66.8%降至39.9%。Raman光谱结果表明,随着CaO添加量的增加,I_D/I_G由1.363增加至1.541,I_G/I_all由0.423减少到0.394。意味着由于Ca的催化作用,煤中大芳香环结构的裂解速率明显增加,且随CaO添加量的增多,煤焦的无序化程度和晶格缺陷均增大。     

东胜长焰煤热解含氧官能团结构演化的13C-NMR和FT-IR分析

以东胜煤田色拉一号井田2号煤层长焰煤为研究对象,利用浮沉离心法富集其镜质组。基于工业分析、元素分析、¹³C-NMR、FT-IR、谱图分峰拟合技术和化学分析测试,求取镜煤及一系列热解煤含氧官能团结构与含量参数,从不同角度研究了含氧官能团的分布规律与演化特点。镜煤中羧基、羰基含量分别为8.91~10.90 mol/kg、1.61~1.79 mol/kg,随热解温度升高羧基显著减少。热解作用促使以端基形式连接在脂肪链或脂肪环结构氧上的甲基和亚甲基首先脱去,且在温度高于350 ℃后基本稳定。氧在热解过程赋存状态的变化是芳香体系与脂肪体系相互竞争的结果,510 ℃热解煤中芳香类氧和脂肪类氧的含量分别为7.49、3.45 mol/kg。羟基的演化过程与热解过程中氧的赋存状态密切相关。随着热解过程的进行,在热解温度低于440 ℃时,各种羟基含量均减少,热解过程对于大分子网络的破坏干扰了各种氢键作用,而羟基π作用则暂时增强,至510 ℃时各种氢键含量均降为最低。东胜长焰煤中含氧官能团化学活性顺序为:[COOH]>[R-O]>[Ar-O-Ar,Ar-O-C,C-O-C]>[C=O]。镜煤非活性醚键含量为0.68 mol/kg,活性醚键为0.48 mol/kg,主要为非活性醚键。     

水蒸气对褐煤原位气化半焦反应性能及微观结构的影响

为了揭示水蒸气对半焦反应性和微观结构的影响,在自制两段新型反应器上依次进行了褐煤干燥、热解及"热"焦的水蒸气原位气化研究。利用TGA、BET和Raman光谱仪,对原位气化半焦进行反应性和微观结构解析。结果表明,在反应温度为600 ℃时,水蒸气对半焦转化率、反应性及微观结构影响很小。温度达到700~900 ℃,在半焦与水蒸气接触的前2 min,虽然半焦转化率变化不大,但其反应性、小环(3~5个芳环)与大环(≥6个环)体系之比及含氧官能团却急剧降低;大于2 min,半焦转化率逐渐增大,反应性、小环与大环之比及含氧官能团缓慢降低;而半焦孔结构在2 min 前后却具有基本一致的变化趋势。半焦与水蒸气接触的前2 min,小环与大环之比和含氧官能团急剧降低是导致反应性显著降低的重要因素,大于2 min,芳环体系的变化是导致反应性进一步降低的原因。     

The Effect of C4H and C5H on the Microstructure of Aqueous Solutions of 1‐Alkyl‐3‐methylimidazolium Tetrafluoroborate Ionic Liquids

As is well‐known, the C2?H proton of 1‐ethyl‐3‐methylimidazolium tetrafluoroborate ([Emim]BF₄) and 1‐butyl‐3‐methylimidazolium tetrafluoroborate ([Bmim]BF₄) has a strong ability to form hydrogen bonds. The purpose of this work is to evaluate the effect of the interactions of the C4?H and C5?H protons on the microstructure of [Emim]BF₄ and [Bmim]BF₄ with water by using ¹H NMR spectroscopy. The differences between the relative ¹H NMR chemical shifts of C2?H, C4?H, and C5?H and between the interaction‐energy parameters obtained from these chemical shifts are minor, thus suggesting that the interactions of C4?H and C5?H may have a considerable effect on the microstructure. To confirm this, the viscosities of the systems are estimated by using the interaction‐energy parameters obtained from the ¹H NMR chemical shifts of the three studied aromatic protons and water, showing that the interactions of C4?H and C5?H also play an important role in the microstructure.     

Synthesis of Nanoporous Ni‐Co Mixed Oxides by Thermal Decomposition of Metal‐Cyanide Coordination Polymers

A straightforward strategy to prepare nanoporous metal oxides with well‐defined shapes is highly desirable. Through thermal treatment and a proper selection of metal‐cyanide coordination polymers, nanoporous nickel‐cobalt mixed oxides with different shapes (i.e., flakes and cubes) can be easily prepared. Our nanoporous materials demonstrate high electrocatalytic activity for oxygen evolution reaction.     

Performance analysis and design of quasi-cyclic LDPC codes for underwater magnetic induction communications

Magnetic induction (MI) communication is an effective scheme for underwater wireless communication. In this paper, we aim to design an underwater MI communication system based on Quasi-cyclic LDPC (QC-LDPC) codes. Firstly, for a given QC-LDPC code used in underwater MI communication, we propose a novel algorithm to evaluate its performance, which is named as underwater magnetic induction protograph (UWMIP) extrinsic information transfer algorithm. Furthermore, we present a differential evolution UWMIP (DE-UWMIP) algorithm, which incorporates the differential evolution method and the UWMIP algorithm. By this algorithm, we search the optimized QC-LDPC codes with best distance threshold. Simulation results show that the proposed algorithm is effective and provide a good guidance to design the underwater MI communication system.     

电化学合成纳米材料和小分子材料在电解制氢领域的应用

氢气是一种清洁、高效、可再生的新型能源,并且是未来碳中和能源供应中最具潜力的化石燃料替代品。因此,可持续氢能源制造具有极大的吸引力与迫切的需求,尤其是通过清洁、环保、零排放的电解水方法。然而,目前的电解水反应受到其缓慢的动力学以及低成本/能源效率的制约。在这些方面,电化学合成通过制造先进的电催化剂和提供更高效/增值的共电解替代品,为提高水电解的效率和效益提供了广阔的前景。它是一种环保、简单的通过电解或其他电化学操作,对从分子到纳米尺度的材料进行制造的方法。本文首先介绍了电化学合成的基本概念、设计方法以及常用方法。然后,总结了电化学合成技术在电解水领域的应用及进展。我们专注于电化学合成的纳米结构电催化剂以实现更高效的电解水制氢,以及小分子的电化学氧化以取代电解水制氢中的析氧共反应,实现更高效、 增值的共电解制氢。我们系统地讨论了电化学合成条件与产物的关系,以启发未来的探索。最后,本文讨论了电化学合成在先进电解水以及其他能量转换和储存应用方面的挑战和前景。     

Optimizing pyrolysis temperature of contaminated rice straw biochar: Heavy metal(loid) deportment,properties evolution,and Pb adsorption/immobilization

Pyrolysis of rice straw (RS), a popular method for producing biochar, effectively treats heavy metal(loid)-contaminated RS. Here, we carried out this process at different temperatures and investigated the deportment of heavy metal(loid)s and the property evolution of biochars. Also, the optimal pyrolysis temperature for Pb adsorption and immobilization was studied. We observed that increasing the temperature could volatilize the heavy metal(loid)s. Cd was the most volatile metal therein, followed by As, while Ni, Cu, and Pb were relatively refractory. More than 75% of the remaining heavy metal(loid)s were non-exchangeable fractions at 700 °C, significantly reducing the environmental risk during subsequent application. Meanwhile, higher pyrolysis temperature resulted in higher pH values, higher surface areas, and stronger Pb adsorption capacity of RS biochars. The maximum adsorption capacity (Q_m) of biochars was in the order of BC300 (77.2 mg·g^?1) < BC500 (137.2 mg·g^?1) < BC700 (222.6 mg·g^?1). Besides, high-temperature biochar could significantly reduce the vertical Pb migration. And BC700 increased the fraction of residual Pb from 39.7% to 44.0% in the soil under the acid rain leaching condition. Therefore, we propose that the heavy metal(loid)-contaminated RS biochar produced at 700 °C might be more suitable for the remediation of soil heavily polluted in the Pb-smelting area.     

Modeling of the Simultaneous Hydrogen Evolution and Cobalt Electrodeposition

A mathematical model of simultaneous cobalt deposition and hydrogen evolution was developed and applied to the electroreduction process of 5 mM Co²⁺ ions investigated by cyclic voltammetry (CV) technique at different hydrogen ion concentrations (pH=2, 3, 4). The kinetic parameters of such a complex process were determined, and the validity of the model and its sensitivity to changes in individual parameters were verified. The relative value of the approximate standard deviation (ASD_%) was used to determine the degree of fit of the model to the experimental data. The catalytic effect of cobalt on the hydrogen evolution process was comprehensively confirmed.