Phosphorus-doped graphene supported palladium (Pd/PG) electrocatalyst for the hydrogen evolution reaction in PEM water electrolysis

PEM water electrolysis is one of the most efficient methods for the production of hydrogen because of produced high purity of the gases and environmentally friendly. In the present study, Phosphorus-doped Graphene (PG) was synthesized by thermal annealing of triphenylphosphine (TPP) and graphene oxide (GO). The PG supported palladium (Pd/PG) electrocatalysts were synthesized by chemical reduction method and used as the cathode for hydrogen evolution reaction (HER) electrode. Structural properties and electrochemical performances of the synthesized Pd/PG electrocatalyst were studied by FE-SEM, EDS, ICP, FT-IR, XRD, and Cyclic voltammetry (CV) methods, respectively. The membrane electrode assemblies (MEA’s) were fabricated using Pd/PG as cathode for HER electrode and RuO₂ as anode for OER electrode. Also, their electrochemical performances along with the corresponding hydrogen yields were evaluated in single cell PEM water electrolyzer at various experimental conditions such as different current densities from 0.1 to 2.0 A cm^?2 and temperatures (28–80°C). The synthesized Pd/PG electrocatalyst was observed a current density of 1 A cm^?2 with 1.95 V at 80°C. Further, long-term stability studies were carried out continuously up to 2000 h which showed a reasonable stability. Hence, the synthesized Pd/PG can be used as an alternative to Pt-based electrocatalysts for the HER in PEM water electrolysis.     

Effects of alkali promoters on the textural and catalytic properties of mesoporous Fe–Al–Cu catalysts for water gas shift reaction

Mesoporous Fe₂O₃–Al₂O₃–CuO catalysts promoted with alkali oxides were synthesized and used in water gas shift reaction (WGSR) at high temperatures for hydrogen purification. These chromium-free catalysts were characterized using nitrogen adsorption/desorption, hydrogen temperature programmed reduction, X-ray diffraction (XRD), and transmission electron microscopy techniques. The synthesized catalysts with narrow single-modal pore size distribution in mesopore region possessed high specific surface area. The catalytic results revealed that except Cs, the addition of other alkali promoters declined the catalytic activity. However, all catalysts showed higher catalytic performance than the conventional commercial catalyst. The results showed an optimum content of Cs promoter (3 wt.%) for the promoted Fe–Al–Cu catalyst (3 wt.% Cs-FAC), which exhibited the highest activity in WGSR at high temperature.     

河流底泥重金属污染与释放特征研究

采用BCR3态连续提取法对底泥中重金属的含量及形态特征进行分析。结果表明，底泥中Cu ， Pb的平均值分别超过背景值的2．45，1．91倍，重金属迁移性的大小为Pb＞Cu＞Cr。研究了底泥中重金属释放特征及影响因素，实验结果表明，Cu的脱附符合二级反应动力学方程拟合，Pb ，Cr的脱附符合抛物线扩散方程和Elovich方程；pH、盐度、温度、泥水比等因素影响重金属的释放量。     

Kinetics of endosulfan sorption on to wood charcoal

Abstract

A part of the research work conducted to evaluate the efficiency of a locally available low cost wood charcoal in removing endosulfan, an organochlorine insecticide, has been presented here in this paper. In the batch experiments conducted at 1 mg/I initial concentration of endosulfan, it was found that wood charcoal could remove endosulfan from water up to 95%. Kinetic profiles were developed for various conditions and they followed second order kinetic reactions. Adsorption equilibrium time was determined by two different approaches namely rough estimate and 2% slope criteria. The equilibrium time was found to be 5 hrs. Forward, reverse, and overall reaction rate constants were determined by approximating the kinetic data to the first order reversible kinetic model. Rate constants increased with increasing initial concentration of endosulfan. Rate limiting process was determined by using kinetics data and further confirmed by the multiple interruption test. Pore and film diffusion coefficients were determined from the half time equations. Film diffusion appeared to be the rate limiting which was further supported by the multiple interruption test.     

Gas-phase thermal explosions in catalytic direct oxidation of alkenes

The metal-based catalytic oxidation of alkenes to the corresponding epoxides is playing a significant role in the modern chemical industry. Nevertheless, these key processes are still lacking proper understanding with respect to the gas-phase runaway behaviour (thermal explosion) and to the hot spot formation on the catalytic surface, under the typical process conditions.This work aims to enlighten these aspects by considering either the catalytic or the gas-phase chemistry for the development of reactor operative diagrams, in order to define the best-operating conditions with respect to the selectivity, the productivity, and the process safety aspects.The proposed methodology has been applied to the oxidation of ethylene and propylene for the direct oxidation process by pure oxygen, considering a detailed kinetic model accounting for the homogeneous reactions, coupled with the heterogeneous catalytic mechanisms.Sensitivity and reaction path analyses were performed to individuate the ruling species and reactions determining the transition to runaway conditions.     

A generalized differential method to calculate lumped kinetic triplet of the nth order model for the global one-step heterogeneous reaction using TG data

Computing kinetic triplet is of importance for the process safety of combustion/gasification industries to establish the chemical reaction scheme and to assess the hazardous risk. Few approaches have been capable of calculating lumped kinetic triplet at one time efficiently, which might be attributed to the fact that the analytical solution for the nonlinear ordinary differential equation (NNODE) for the n^th order reaction model has not been found yet. This paper presents an analytical solution of NNODE to compute kinetic triplet. Results showed that the proposed method (mass fraction curve-fitting error ϕ = 1.49%–2.07%) is more efficient to compute kinetic triplet of the n^th order reaction model, comparing to genetic algorithm (GA) optimization (ϕ = 1.43%–1.81%), Coats-Redfern (ϕ = 2.36%–3.16%), peak-shape, and isoconversional methods. A compensation effect between lnA and E_a is observed due to heating rates. Effects of exported data quality and smooth processing on computation of kinetic triplet are discussed. It is the first time that an analytical solution of NNODE (n^th order model) for global one-step heterogeneous reaction is derived for computing kinetic triplet. This work may help to search for analytical solutions of power-law and Avrami-Erofeev models in the future to efficiently calculate kinetic triplet for accelerating and sigmoidal reaction systems.     

新显色剂NPBPDT的合成及在环境监测中的应用研究

研究了1(4硝基苯基)3(5溴吡啶)三氮烯(NPBPDT)的合成及其与汞的显色反应。在TX100存在下,pH值为11.5的Na2B4O7NaOH缓冲溶液中,该试剂能与汞发生显色反应,汞与NPBPDT形成摩尔比为1∶2型的黄色配合物,在440nm处有一最大正吸收峰,在535nm处有一最大负吸收。以440nm为参比波长,535nm为测量波长进行双波长测定,表观摩尔吸光系数为2.80×105Lmol·cm,汞的浓度在0～12μg25mL范围内符合比尔定律。用拟定方法测定废水中的微量汞,有较高的准确度和精密度。     

内电解还原-高效厌氧反应工艺处理化工生产废水

化工生产废水中有机物浓度高,成分复杂,采用常规的处理工艺难以达标。本工艺采用分级处理的方法,先通过催化氧化、内电解铁屑还原反应装置,降低生产浓废水中的有机物含量,改善污水的可生化性;再采用高效厌氧反应器进一步处理废水,有机物去除率高,出水水质稳定,实现了达标排放。     

2-n-丙基酚在模拟海水中的耗氧特性及降解动力学

以2-n-丙基酚为研究对象,分3个质量浓度系列研究其在人工模拟海水中的耗氧特性及降解过程.试验结果表明,在该模拟海水体系中,ρ(DO)呈现先下降后上升的趋势,ρ(DO)变化过程与2-n-丙基酚的生物降解过程密切相关,ρ(DO)最低值出现在2-n-丙基酚降解率达85%～90%的阶段.2-n-丙基酚在该体系中的生物降解反应符合一级反应动力学规律,其生物降解速率与2-n-丙基酚初始质量浓度有关.2-n-丙基酚初始质量浓度增加,生物降解速率下降,滞后期和半衰期也相应延长.      

厌氧氨氧化菌的培养与推流式反应器氨厌氧工艺

采用推流式固定化絮体生物反应器培养出高活性的厌氧氨氧化(ANAMMOX)红色颗粒污泥.在稳定运行后,反应器的NH₄⁺-N和NO₂^--N去除率皆大于98%,TN平均去除率为86%,NO₃^--N的生成率约为14%,TN去除负荷达2.56kg/(m³·d).同时考察了进水基质比例对反应器性能的影响,并用扫描电镜观察了颗粒结构.