Preparation of birnessite-supported Pt nanoparticles and their application in catalytic oxidation of formaldehyde

Flaky and nanospherical birnessite and birnessite-supported Pt catalysts were successfully prepared and characterized by means of X-ray diffraction (XRD), transmission electron microscopy (TEM), energy dispersive spectroscopy (EDS) and N₂ adsorption-desorption. Effects of the birnessite morphology and Pt reduction method on the catalytic activity for the complete oxidation of formaldehyde (HCHO) were investigated. It was found that flaky birnessite exhibited higher catalytic activity than nanospherical birnessite. The promoting effect of Pt on the birnessite catalyst indicated that the reduction method of the Pt precursor greatly influenced the catalytic performance. Flaky birnessite-supported Pt nanoparticles reduced by KBH₄ showed the highest catalytic activity and could completely oxidize HCHO into CO₂ and H₂O at 50℃, whereas the sample reduced using H₂-plasma showed lower activity for HCHO oxidation. The differences in catalytic activity of these materials were jointly attributed to the effects of pore structure, surface active sites exposed to HCHO and the dispersion of Pt nanoparticles.     

Insight into phase structure-dependent soot oxidation activity of K/MnO2 catalyst

In the present study, two nanosized MnO₂ with β and δ phase structures and potassium loaded MnO₂ catalysts with varied K loading amounts (denoted as K/MnO₂) were prepared. Temperature programmed oxidation and isothermal reactions in loose contact modes were employed to examine the soot oxidation activity of the as-prepared catalysts. Characterization results show that as compared with β-MnO₂, δ-MnO₂ has larger surface area and higher content of hydroxyl groups. Upon K loading, abundant hydroxyl groups in δ-MnO₂ effectively sequestrate K cation to form bound K species and free K species are available only at K loading above 3.0 wt.%. In contrast, the majority of K species present as free state in β-MnO₂ even at a K loading of 1.0 wt.% due to its very low hydroxyl group content. The O₂ temperature-programmed desorption (O₂-TPD) demonstrates that the catalysts with free K species exhibit strong ability in activating gaseous O₂, whereas the catalysts only having bound K display minor O₂ activation capability. As a result, despite of slightly lower activity of β-MnO₂ than δ-MnO₂, the K/β-MnO₂ catalysts exhibit substantially higher activities than K/δ-MnO₂ catalysts with identical K loadings. The finding in this study clearly demonstrates that for MnO₂ based catalysts, the enhancement of catalytic activity for soot oxidation is highly K loading amount dependent and the dependency is strongly associated with the phase structure of MnO₂.     

Promotional effect of cobalt doping on catalytic performance of cryptomelane-type manganese oxide in toluene oxidation

The cryptomelane-type manganese oxide (OMS-2)-supported Co (xCo/OMS-2; x = 5, 10, and 15 wt.%) catalysts were prepared via a pre-incorporation route. The as-prepared materials were used as catalysts for catalytic oxidation of toluene (2000 ppmV). Physical and chemical properties of the catalysts were measured using the X-ray diffraction (XRD), Fourier transform infrared spectroscopic (FT-IR), scanning electron microscopic (SEM), X-ray photoelectron spectroscopy (XPS), and hydrogen temperature-programmed reduction (H₂-TPR) techniques. Among all of the catalysts, 10Co/OMS-2 performed the best, with the T_90%, specific reaction rate at 245°C, and turnover frequency at 245°C (TOF_Co) being 245°C, 1.23 × 10⁻³ mol_toluene/(g_cat·sec), and 11.58 × 10⁻³ sec⁻¹ for toluene oxidation at a space velocity of 60,000 mL/(g·hr), respectively. The excellent catalytic performance of 10Co/OMS-2 were due to more oxygen vacancies, enhanced redox ability and oxygen mobility, and strong synergistic effect between Co species and OMS-2 support. Moreover, in the presence of poisoning gases CO₂, SO₂ or NH₃, the activity of 10Co/OMS-2 decreased for the carbonate, sulfate and ammonia species covered the active sites and oxygen vacancies, respectively. After the activation treatment, the catalytic activity was partly recovered. The good low-temperature reducibility of 10Co/OMS-2 could also facilitate the redox process accompanied by the consecutive electron transfer between the adsorbed O₂ and the cobalt or manganese ions. In the oxidation process of toluene, the benzoic and aldehydic intermediates were first generated, which were further oxidized to the benzoate intermediate that were eventually converted into H₂O and CO₂.     

Surface characterization of metal oxides-supported activated carbon fiber catalysts for simultaneous catalytic hydrolysis of carbonyl sulfide and carbon disulfide

The sol–gel method was used to synthesize a series of metal oxides-supported activated carbon fiber (ACF) and the simultaneous catalytic hydrolysis activity of carbonyl sulfide (COS) and carbon disulfide (CS₂) at relatively low temperatures of 60°C was tested. The effects of preparation conditions on the catalyst properties were investigated, including the kinds and amount of metal oxides and calcination temperatures. The activity tests indicated that catalysts with 5 wt.% Ni after calcining at 400°C (Ni(5)/ACF(400)) had the best performance for the simultaneous catalytic hydrolysis of COS and CS₂. The surface and structure properties of prepared ACF were characterized by scanning electron microscope-energy disperse spectroscopy (SEM-EDS), Brunauer–Emmett–Teller (BET), X-ray diffraction (XRD), carbon dioxide-temperature programmed desorption (CO₂-TPD) and diffuse reflectance Fourier transform infrared reflection (DRFTIR). And the metal cation defects were researched by electron paramagnetic resonance (EPR) method. The characterization results showed that the supporting of Ni on the ACF made the ACF catalyst show alkaline and increased the specific surface area and the number of micropores, then improved catalytic hydrolysis activity. The DRFTIR results revealed that -OH species could facilitate the hydrolysis of COS and CS₂; -COO and -C–O species could facilitate the oxidation of catalytic hydrolysate H₂S. And the EPR results showed that high calcination temperature conditions provide more active reaction center for the COS and CS₂ adsorption.     

Enhanced catalytic complete oxidation of 1,2-dichloroethane over mesoporous transition metal-doped γ-Al2O3

High-surface-area mesoprous powders of γ-Al₂O₃ doped with Cu²⁺, Cr³⁺, and V³⁺ ions were prepared via a modified sol-gel method and were investigated as catalysts for the oxidation of chlorinated organic compounds. The composites retained high surface areas and pore volumes comparable with those of undoped γ-Al₂O₃ and the presence of the transition metal ions enhanced their surface acidic properties. The catalytic activity of the prepared catalysts in the oxidation of 1,2-dichloroethane (DCE) was studied in the temperature range of 250-400℃. The catalytic activity and product selectivity were strongly dependent on the presence and the type of dopant ion. While Cu²⁺- and Cr³⁺-containing catalysts showed 100% conversion at 300℃ and 350℃, V³⁺-containing catalyst showed considerably lower conversion. Furthermore, while the major products of the reactions over γ-alumina were vinyl chloride (C₂H₃Cl) and hydrogen chloride (HCl) at all temperatures, Cu- and Cr-doped catalysts showed significantly stronger capability for deep oxidation to CO₂.     

Investigation of suitable precursors for manganese oxide catalysts in ethyl acetate oxidation

The control of ethyl acetate emissions from fermentation and extraction processes in the pharmaceutical industry is of great importance to the environment. We have developed three Mn₂O₃ catalysts by using different Mn precursors (MnCl₂, Mn(CH₃COO)₂, MnSO₄), named as Mn₂O₃-Cl, -Ac, -SO₄. The tested catalytic activity results showed a sequence with Mn precursors as: Mn₂O₃-Cl > Mn₂O₃-Ac > Mn₂O₃-SO₄. The Mn₂O₃-Cl catalyst reached a complete ethyl acetate conversion at 212℃ (75℃ lower than that of Mn₂O₃-SO₄), and this high activity 100% could be maintained high at 212℃ for at least 100 hr. The characterization data about the physical properties of catalysts did not show an obvious correlation between the structure and morphology of Mn₂O₃ catalysts and catalytic performance, neither was the surface area the determining factor for catalytic activity in the ethyl acetate oxidation. Here we firstly found there is a close linear relationship between the catalytic activity and the amount of lattice oxygen species in the ethyl acetate oxidation, indicating that lattice oxygen species were essential for excellent catalytic activity. Through H₂ temperature-programmed reduction (H₂-TPR) results, we found that the lowest initial reduction temperature over the Mn₂O₃-Cl had stronger oxygen mobility, thus more oxygen species participated in the oxidation reaction, resulting in the highest catalytic performance. With convenient preparation, high efficiency, and stability, Mn₂O₃ prepared with MnCl₂ will be a promising catalyst for removing ethyl acetate in practical application.     

Catalytic activity of porous manganese oxides for benzene oxidation improved via citric acid solution combustion synthesis

Various manganese oxides (MnO_x) prepared via citric acid solution combustion synthesis were applied for catalytic oxidation of benzene. The results showed the ratios of citric acid/manganese nitrate in synthesizing process positively affected the physicochemical properties of MnO_x, e.g., BET (Brunauer-Emmett-Teller) surface area, porous structure, reducibility and so on, which were in close relationship with their catalytic performance. Of all the catalysts, the sample prepared at a citric acid/manganese nitrate ratio of 2:1 (C2M1) displayed the best catalytic activity with T₉₀ (the temperature when 90% of benzene was catalytically oxidized) of 212℃. Further investigation showed that C2M1 was Mn₂O₃ with abundant nano-pores, the largest surface area and the proper ratio of surface Mn⁴⁺/Mn³⁺, resulting in preferable low-temperature reducibility and abundant surface active adsorbed oxygen species. The analysis results of the in-situ Fourier transform infrared spectroscopy (in-situ FTIR) revealed that the benzene was successively oxidized to phenolate, o-benzoquinone, small molecules (such as maleates, acetates, and vinyl), and finally transformed to CO₂ and H₂O.     

Effect of pretreatment on Pd/Al2O3 catalyst for catalytic oxidation of o-xylene at low temperature

The effect of pretreatment on Pd/Al₂O₃ catalysts for the catalytic oxidation of o-xylene at low temperature was studied by changing the pretreatment and testing conditions. The fresh and pretreated Pd/Al₂O₃ catalysts were characterized by transmission electron microscopy (TEM), X-ray photoelectron spectroscopy (XPS) and X-ray diffraction (XRD). The results showed that the pretreatment dramatically changed the Pd/PdO ratio and then significantly affected the Pd/Al₂O₃ activity; while the pretreatment had not much influence on Pd particle size. The Pd/Al₂O₃ pre-reduced at 300℃/400℃, which has fully reduced Pd species, showed the highest activity; while the fresh Pd/Al₂O₃, which has fully oxidized Pd species, presented the worst performance, indicating the Pd chemical state plays an important role in the catalytic activity for the o-xylene oxidation. It is concluded that metallic Pd is the active species on the Pd/Al₂O₃ catalyst for the catalytic oxidation of o-xylene at low temperature.     

Effect of different reduction methods on Pd/Al2O3 for o-xylene oxidation at low temperature

Pd/Al₂O₃ was pretreated by CO, H₂ and NaBH₄ reduction, respectively. The reduced catalysts were tested for o-xylene oxidation and characterized by power X-ray diffraction (XRD), transmission electron microscopy (TEM), X-ray photoelectron spectroscopy (XPS) and temperature-programmed decomposition of palladium hydride (TPDH). The characterizations indicate the pretreatments lead to distinct Pd particle sizes and amount of surface activated oxygen species, which are responsible for the catalytic performance. Compared with H₂ and NaBH₄ reduction methods, CO reduction shows a strong interaction between Pd and Al₂O₃ with smaller Pd particle size and more surface activated oxygen. It exhibited excellent catalytic performance, complete oxidation of 50 ppmV o-xylene at 85°C with a WHSV of 60,000 mL/(g∙hr).     

Degradation mechanism of Direct Pink 12B treated by iron-carbon micro-electrolysis and Fenton reaction

The Direct Pink 12B dye was treated by iron-carbon micro-electrolysis (ICME) and Fenton oxidation. The degradation pathway of Direct Pink 12B dye was inferred by ultraviolet visible (UV-Vis), infrared absorption spectrum (IR) and high performance liquid chromatography-mass spectrometry (HPLC-MS). The major reason of decolorization was that the conjugate structure was disrupted in the iron-carbon micro-electrolysis (ICME) process. However, the dye was not degraded completely because benzene rings and naphthalene rings were not broken. In the Fenton oxidation process, the azo bond groups surrounded by higher electron cloud density were first attacked by hydroxyl radicals to decolorize the dye molecule. Finally benzene rings and naphthalene rings were mineralized to H₂O and CO₂ under the oxidation of hydroxyl radicals.     

关于对烟花爆竹行业开征环境税问题探讨研究

如今燃放烟花爆竹所带来的环境问题已经日益明显,特别是对环境空气质量的影响。在当今雾霾笼罩的大氛围下,对烟花爆竹的生产和销售、消费领域采取适当环境经济手段来调控(如征收环境税)就显得很有必要,这在一定程度上可以控制烟花爆竹的消费量,减少燃放烟花爆竹所造成的环境外部性。同时用征收来的环境税对研发采用环保药剂、先进技术的企业进行补贴、奖励,或者对于这些企业给予一定的环境税优惠,可以引导烟花爆竹产业朝着更加健康的方向发展。     

《控制船舶有害防污底系统国际公约》及有关问题探讨

介绍了《控制船舶有害防污底系统国际公约》产生的历史背景和基本内容，论述了中国加入该公约的必要性及对中国产生的影响，并提出中国加入控制船舶有害防污底系统国际公约后对策和建议。     

液化石油气推广应用的可行性研究

城市交通带来的大气污染问题日趋严重，为解决这一问题，国内外科研人员进行了数十年的开发研究，液化石油替代传统燃料作为机动车动力源已被认为是解决城市机动车尾气污染行之有效的办法，该方法集环保、经济、安全等优点，是未来汽车工业发展的方向。本文针对目前我国城市大气污染现状，分析比较现有防治对策措施，对液化气汽车在国内推广应用的可行性进行了简单阐述。     

黄土高原南部土壤退化机理研究

黄土高原土壤侵蚀极其严重 ,这不仅导致了土壤生产力的降低 ,同时也导致了土壤的退化。本文在定位监测、室内分析及野外调查的基础上 ,研究了黄土高原南部土壤的退化机理。结果表明 :土壤中 <0 0 1mm颗粒和土壤养分流失是造成黄土高原土壤退化的主要原因 ,耕地土壤结构状况的恶化和土壤酶的流失使土壤退化程度进一步加剧 ,从而成为严重制约该区经济发展障碍。     

基于AHP-模糊综合评价的LNG接收站安全评价

介绍了一种基于层次分析法和模糊综合评价的LNG接收站的安全评价方法,根据LNG接收站工艺、环境等特点,建立LNG接收站安全评价指标,根据评价指标间的关系构造指标的判断矩阵,求出对应指标系统的权重,对指标进行评价。根据对国内某接收站的安全评价,提出相应的整改措施。     

交通源重金属污染研究进展

随着我国经济社会、高速公路的飞速发展,居民人均拥有汽车及机动车保有量都大大增加了,研究交通源重金属污染显得越来越重要。本文介绍了交通源重金属的来源,对交通源重金属的排放量及影响因素、公路旁各环境介质中的重金属、重金属的形态和生物有效性、重金属对人体健康的影响进行了综述。为交通源重金属污染的研究提供了一定的思路。     

基于低影响开发的雨洪管理研究现状和趋势研究

降雨径流是影响城市河流水质以及发生内涝的主要原因之一,传统的雨水管理模式已经不能适应现代城市的发展,低影响开发是基于模拟自然水文状况的原理,采用源头控制来消减、利用和延缓径流以及控制径流污染的一种分散的、多样性的、景观化的微型控制单元。国内低影响开发的工程实践还比较少,在借鉴国外有关低影响开发的设计方法、效果监测以及模型模拟方面的理论同时,国内还需要开展长期效果监测来建立自己的设计参数数据库以及研究适合国内的设计决策支持工具。     

丘陵道路下实际行驶污染物排放研究

为研究丘陵道路特征对实际行驶排放（RDE）试验中污染物排放和动力学特性校验的影响,本文利用一辆轻型汽油车,在重庆地区满足国六排放法规要求的4条不同道路特征的路线上各进行了两次RDE试验.结果表明：CO₂与道路坡度呈显著线性相关,坡度每增加1%,CO₂排放因子平均增加22.4%,CO和PN则与道路坡度呈二次多项式关系,NO_x与坡度无明显相关性.从移动平均窗口层面对比考虑坡度的VSP_pos[95]（路段中正比功率升序排列的第95个百分位值）和不考虑坡度的v·a_pos[95]（速度与正加速乘积升序排列的第95个百分位值）与PN的关系,发现窗口VSP_pos[95]和v·a_pos[95]与PN的二次拟合R2平均值分别为0.93和0.72,当窗口累计正海拔增量大于600 m/100 km时,VSP_pos[95]与PN的相关性明显优于v·a_pos[95],建议在累计正海拔增量大于600 m/100 km的...     

环状糊精在生物法处理废水中的应用

用生物法进行污水的处理，因其环保高效的优点而被广泛应用。但是，废水中的毒性超过一定浓度，生物淤泥的脱毒能力会受到不可恢复的损害。概述了环状糊精的结构、性质以及国内外的研究进展；将环状糊精应用于生物法废水处理，以其特有的结构特点可解决上述问题。