High-performance Si-Containing anode materials in lithium-ion batteries:A superstructure of Si@Co–NC composite works effectively

To mitigate the massive volume expansion of Si-based anode during the charge/discharge cycles, we synthesized a superstructure of Si@Co–NC composite via the carbonization of zeolite imidazolate frameworks incorporated with Si nanoparticles. The Si@Co–NC is comprised of Si-nanoparticle core and N-doped/Co-incorporated carbon shell, and there is void space between the core and the shell. When using as anode material for LIBs, Si@Co–NC displayed a super performance with a charge/discharge capacity of 191.6/191.4 mA h g-1 and a coulombic efficiency of 100.1％ at 1000 mA g-1 after 3000 cycles, and the capacity loss rate is 0.022％ per cycle only. The excellent electrochemical property of Si@Co–NC is because its electronic conductivity is enhanced by doping the carbon shell with N atoms and by incorporating with Co particles, and the pathway of lithium ions transmission is shortened by the hollow structure and abundant mesopores in the carbon shell. Also, the volume expansion of Si nanoparticles is well accommodated in the void space and suppressed by the carbon host matrix. This work shows that, through designing a superstructure for the anode materials, we can synergistically reduce the work function and introduce the confinement effect, thus significantly enhancing the anode materials' electrochemical performance in LIBs.     

基于Tenax脱附技术评价沉积物中不同碳质对菊酯类农药生物有效性的影响研究

本文选取泥炭、生物质炭、木炭和活性炭4种含碳材料,结合以经济底栖生物菲律宾蛤仔(Venerupis philippinarum)为受试生物的生物累积实验和Tenax连续萃取法,阐述不同碳质对沉积物中4种菊酯类农药生物有效性的影响,并将Tenax萃取结果与底栖生物的累积结果进行了相关分析。结果表明,碳质的添加导致沉积物中菊酯类农药的快速脱附组分(Frap)降低,极慢速脱附组分(Fv s)增大,生物有效性降低,且4种碳质对Frap的影响有所不同,然而因为菊酯类农药的理化性质,Frap的差异并不显著。Tenax 6 h和24 h的单点萃取组分与快速脱附组分相关性显著(P0.0001),基本可以代替完整的脱附动力学评价生物有效性,但是对于组成复杂,有机碳(OC)和黑炭(BC)含量高的沉积物进行研究评价时仍应注意由此产生的偏离。Tenax快速脱附组分与2种底栖生物累积结果之间具有显著的相关性(R2=0.38,P0.0001),表明在OC和BC含量不同的沉积物中,Tenax萃取技术也可以预测菊酯类农药在经济底栖生物菲律宾蛤仔体内的累积量,进而为沉积物中HOCs的环境质量和相关水产品的质量评估提供更为快捷、有效的参考依据。     

基于席夫碱反应合成氮掺杂的碳活化PMS降解双酚A

基于石墨相氮化碳(g-C3N4)的热聚合形成过程和席夫碱反应,本文将尿素和2-萘甲醛作为前驱体,经一步热聚合反应制备了氮掺杂的碳材料(NCN-x),并以其作为催化剂活化过一硫酸盐(PMS)来降解双酚A(BPA).在催化剂特性研究部分,利用SEM、XRD、FTIR以及XPS对其表面形貌、结构与元素组成进行分析.结果 表明...     

Insight into the promotion mechanism of activated carbon on the monolithic honeycomb red mud catalyst for selective catalytic reduction of NOx

• Activated carbon was proposed to be an efficient accelerant for molded red mud catalyst. • The surface acidity and reducibility were highly improved, as well as the pore structure. • The enrichment of the surface Fe²⁺ and the adsorbed oxygen account for the improvement. Our previous study proved that the acid-pretreatment process could efficiently activate red mud (RM) for the selective catalytic reduction (SCR) of NO_x. However, in terms of the molding process, which is the key step determining whether it can be applied in large-scale industrial, the surface acidity and reducibility of catalyst always decreased dramatically, and part of surface area and pore structure were lost. In this study, we prepared monolithic honeycomb red mud (MHRM) catalysts with activated carbon (AC) as an accelerant and investigated the effect of AC on the MHRM. The results showed that the MHRM with 3 wt.% of AC (MHRM-AC3) exhibited the best SCR performance, and kept more than 80% NO_x conversion in the range of 325°C–400°C. Compared with the MHRM, MHRM-AC1, and HMRM-AC5, the MHRM-AC3 has more mesoporous and macroporous structures, which can provide more adsorption active sites. The AC significantly improved NH₃ adsorption and surface reducibility, which was mainly due to the increase of the surface acid sites (especially the Brönsted acid sites), the concentration of Fe(II), and the surface adsorbed oxygen. The presence of more Fe(II) enriched the surface oxygen vacancies, as well as the surface adsorbed oxygen, due to the charge imbalance and unsaturated chemical bond. And surface adsorbed oxygen exhibited more active than lattice oxygen owing to its higher mobility, which was conducive to NO_x reduction in the SCR reaction.     

Effect of Cu-ZSM-5 catalysts with different CuO particle size on selective catalytic oxidation of N,N-Dimethylformamide

● A series of Cu-ZSM-5 catalysts were tested for DMF selective catalytic oxidation. ● Cu-6 nm samples showed the best catalytic activity and N₂ selectivity. ● Redox properties and chemisorbed oxygen impact on DMF catalytic oxidation. ● Isolated Cu²⁺ species and weak acidity have effects on the generation of N₂. N, N-Dimethylformamide (DMF), a nitrogen-containing volatile organic compound (NVOC) with high emissions from the spray industry, has attracted increasing attention. In this study, Cu-ZSM-5 catalysts with different CuO particle sizes of 3, 6, 9 and 12 nm were synthesized and tested for DMF selective catalytic oxidation. The crystal structure and physicochemical properties of the catalyst were studied by various characterization methods. The catalytic activity increases with increasing CuO particle size, and complete conversion can be achieved at 300–350 °C. The Cu-12 nm catalyst has the highest catalytic activity and can achieve complete conversion at 300 °C. The Cu-6 nm sample has the highest N₂ selectivity at lower temperatures, reaching 95% at 300 °C. The activity of the catalysts is determined by the surface CuO cluster species, the bulk CuO species and the chemisorbed surface oxygen species. The high N₂ selectivity of the catalyst is attributed to the ratio of isolated Cu²⁺ and bulk CuO species, and weak acidity is beneficial to the formation of N₂. The results in this work will provide a new design of NVOC catalytic oxidation catalysts.     

Conversion of waste plastics into value-added carbon materials

Plastic pollution is a major environmental issue worldwide, calling for advanced methods to recycle waste plastics in the context of the circular economy. Here we review methods and strategies to convert waste plastics into value-added carbon materials, with focus on sources, properties, pretreatment of waste plastics, and on preparation of carbon materials. Pretreatment techniques include mechanical crushing, plastic stabilization and electrospinning. Carbon materials such as carbon nanotubes, graphene, carbon nanosheets, carbon spheres and porous carbon are prepared by oxygen-limited carbonization, catalytic carbonization, the template-based method, and pressure carbonization. We emphasize the conversion of polyethene terephthalate, polyethylene, polypropylene, polystyrene, halogenated plastics, polyurethane and mixed plastics.

     

六铝酸盐负载CuO催化还原NO性能

采用共沉淀法制备了LaAl12O19六铝酸盐载体,采用等体积浸渍法制备了不同负载量的CuO/LaAl12O19催化剂,并对其进行了XRD、H2-TPR和BET表征,考察了催化剂对CH4选择催化还原NO的性能.结果表明,CuO的负载并未改变六铝酸盐载体的结构,Cu在载体上以Cu2+的形式存在,活性组分CuO与载体LaAl12O19之间存在协同作用;CuO/LaAl12O19催化剂对CH4选择催化还原NO表现出良好活性,所制备的催化剂均能使NO的转化率达到99%;其中负载量为1.0 wt%的CuO/LaAl12O19催化剂的活性最好,完全反应温度T99%为560℃,且在80 h稳定性试验中表现出了良好的高温活性和热稳定性.     

活性炭催化剂上SO2转化活性中心的研究

研究了用不同原料及不同方法制备的活性炭催化剂物化性质变化及其与SO_2转化为SO_3的催化活性的关系。结果表明,催化剂的活性主要取决于其表面性质,而与其孔结构等物理性质无明显关系。XPS和TPD结果认为,催化剂表面上存在有五种数量不等的基团,即(酮基),(烯酮基),其中,含氧基团=C=O为SH_2转化为SO_3的活性中心,可以经改质手段使糠醛渣活性炭上该基团数量增加,从而可提高催化活性。     

Room-temperature solid phase surface engineering of BiOI sheets stacking g-C3N4 boosts photocatalytic reduction of Cr(VI)

Cr(VI)-based compounds pollution have attracted global concern due to serious harm to humans and environment. Hence, it is crucial to exploit an effective technique to eliminate Cr(VI) in water. Herein, we in-situ grown BiOI on graphitic carbon nitride to prepare the BiOI/g-C3N4 (BCN) direct Z-scheme heterojunction by solid phase engineering method at room temperature. Experimental result shown the photocatalytic activity of pure BiOI were obviously enhanced by constructing Z-scheme BCN heterostructure, and BCN-3 heterostructure exhibited the optimal photocatalytic degradation of RhB with 98％yield for 2.5 h and reduction of Cr(VI) with more than 99％yield for 1.5 h at pH=2. Stability test shows BCN-3 still kept more than 98％reduction efficiency after 6 cycles. In addition, we also studied the reduction mechanism that shown the ·O2-radicals essentially helped to reduce the Cr(VI) in aqueous solution under illumination, verified the direct Z-scheme charge transfer path by X-ray photoelectron spectroscopy (XPS) and the free radical trapping experiment. The work open a new way for rationally designing photo-catalyst heterostructure to reduce Cr(VI) to Cr(III).     

Precise regulation of acid pretreatment for red mud SCR catalyst: Targeting on optimizing the acidity and reducibility

• The optimum SCR activity was realized by tuning the acid pretreatment. • Optimized catalysts showed NO_x conversion above 90%. • The NH₃ and NO adsorption capacity of Al-O₃-Fe is stronger than Fe-O₃-Fe. • The formation of almandine consumes Fe³⁺ and Al³⁺ and weakens their interaction. Red mud (RM), as an alkaline waste, was recently proved to be a promising substitute for the SCR catalyst. Dealkalization could improve the acidity and reducibility of red mud, which were critical for SCR reaction. However, the dealkalization effect depended on the reaction between acid solution and red mud. In this study, we realized the directional control of the chemical state of active sites through tuning the acid pretreatment (dealkalization) process. The pretreatment endpoint was controlled at pH values of 3–5 with diluted nitric acid. When the pH values of red mud were 3 and 5 (CRM-3 and CRM-5), activated catalysts showed NO_x conversion above 90% at 275°C–475°C. The high initial reaction rate, Ce³⁺/(Ce³⁺ + Ce⁴⁺) ratio, and surface acidity accounted for the excellent SCR performance of CRM-5 catalyst. Meanwhile, more Fe³⁺ on the CRM-3 surface improved the NH₃ adsorption. There was a strong interaction between Al and Fe in both CRM-5 and CRM-3 catalysts. DFT results showed that the adsorption capacity of the Al-O₃-Fe for NH₃ and NO is stronger than that of Fe-O₃-Fe, which enhanced the NO_x conversion of the catalyst. However, the almandine was formed in CRM-4, consumed part of Fe³⁺ and Al³⁺, and the interaction between Al and Fe was weakened. Also, deposited almandine on the catalyst surface covered the active sites, thus leading to lower NH₃-SCR activity.     

Synthesis, physicochemical characterizations and catalytic performance of Pd/carbon-zeolite and Pd/carbon-CeO2 nanocatalysts used for total oxidation of xylene at low temperatures

In this work, xylene removal from waste gas streams was investigated via catalytic oxidation over Pd/carbon-zeolite and Pd/carbon-CeO₂ nanocatalysts. Activated carbon was obtained from pine cone chemically activated using ZnCl₂ and modified by H₃PO₄. Natural zeolite of clinoptilolite was modified by acid treatment with HCl, while nano-ceria was synthesized via redox method. Mixed supports of carbon-zeolite and carbonceria were prepared and palladium was dispersed over them via impregnation method. The prepared samples were characterized by X-ray diffraction (XRD), field emission scanning electron microscopy (FESEM), Brunauer-Emmett-Teller surface area (BET), Fourier transform infrared spectroscopy (FTIR) and thermogravimetric (TG) techniques. Characterization of nanocatalysts revealed a good morphology with an average particle size in a nano range, and confirmed the formation of nano-ceria with an average crystallite size below 60 nm. BET analysis indicated a considerable surface area for catalysts (～1000 m²·g^?1). FTIR patterns demonstrated that the surface groups of synthesized catalysts are in good agreement with the patterns of materials applied in catalyst synthesis. The performance of catalysts was assessed in a low-pressure catalytic oxidation pilot in the temperature range of 100° C-250°C. According to the reaction data, the synthesized catalysts have been shown to be so advantageous in the removal of volatile organic compounds (VOCs), representing high catalytic performance of 98% for the abatement of xylene at 250°C. Furthermore, a reaction network is proposed for catalytic oxidation of xylene over nanocatalysts.     

Tailoring the simultaneous abatement of methanol and NOx on Sb-Ce-Zr catalysts via copper modification

● Cu addition enhances CH₃OH oxidation and alleviates its inhibitory effect on SCR. ● Cu addition improves the activation of SCR reactants in the presence of methanol. ● Damaged structure by more Cu addition decreases specific surface area and acidity. ● Excessive Cu addition would lead to the narrowing of SCR temperature window. Simultaneously removal of NO_x and VOCs over NH₃-SCR catalysts have attracted lots of attention recently. However, the presence of VOCs would have negative effect on deNO_x efficiency especially at low temperature. In this study, copper modification onto Sb_0.5CeZr₂O_x (SCZ) catalyst were performed to enhance the catalytic performance for simultaneous control of NO_x and methanol. It was obtained that copper addition could improve the low-temperature activity of both NO_x conversion and methanol oxidation, where the optimal catalyst (Cu_0.05SCZ) exhibited a deNO_x activity of 96% and a mineralization rate of 97% at 250 °C, which are around 10% higher than that of Cu free sample. The characterization results showed that copper addition could obviously enhance the redox capacity of the catalysts. As such, the inhibition effect of methanol incomplete oxidation on NO adsorption and NH₃ activation were then lessened and the conversion of surface formamide species were also accelerated, resulting in the rising of NO_x conversion at low temperature. However, excessive copper addition would damage the Sb-Ce-Zr oxides solid solution structure owing to Cu-Ce strong interactions, decreasing the surface area and acidity. Meanwhile, due to easier over-oxidation of NH₃ with more Cu addition, the temperature window for NO_x conversion would become quite narrow. These findings could provide useful guidelines for the synergistic removal of VOCs over SCR catalyst in real application.     

Sulfonated graphene nanomaterials for membrane antifouling,pollutant removal,and production of chemicals from biomass: a review

Water pollution and the unsustainable use of fossil fuel derivatives require advanced catalytic methods to clean waters and to produce fine chemicals from modern biomass. Classical homogeneous catalysts such as sulfuric, phosphoric, and hydrochloric acid are highly corrosive and non-recyclable, whereas heterogeneous catalysts appear promising for lignocellulosic waste depolymerization, pollutant degradation, and membrane antifouling. Here, we review the use of sulfonated graphene and sulfonated graphene oxide nanomaterials for improving membranes, pollutant adsorption and degradation, depolymerization of lignocellulosic waste, liquefaction of biomass, and production of fine chemicals. We also discuss the economy of oil production from biomass. Sulfonated graphene and sulfonated graphene oxide display an unusual large theoretical specific surface area of 2630 m²/g, allowing the reactants to easily enter the internal surface of graphene nanosheets and to reach active acid sites. Sulfonated graphene oxide is hydrophobic and has hydrophilic groups, such as hydroxyl, carboxyl, and epoxy, thus creating cavities on the graphene nanosheet’s surface. The adsorption capacity approached 2.3–2.4 mmol per gram for naphthalene and 1-naphthol. Concerning membranes, we observe an improvement of hydrophilicity, salt rejection, water flux, antifouling properties, and pollutant removal. The nanomaterials can be reused several times without losing catalytic activity due to the high stability originating from the stable carbon–sulfur bond between graphene and the sulfonic group.

     

Enhanced performances in catalytic oxidation of <Emphasis Type="Italic">o</Emphasis>-xylene over hierarchical macro-/mesoporous silica-supported palladium catalysts

A series of hierarchical macro-/mesoporous silica supports (MMSs) were successfully synthesized using dual-templating technique employing polystyrene (PS) spheres and the Pluronic P123 surfactant. Pd was next loaded on the hierarchical silica supports via colloids precipitation method. Physicochemical properties of the synthesized samples were characterized by various techniques and all catalysts were tested for the total oxidation of o-xylene. Among them, the Pd/MMS-b catalyst with tetraethoxysilane/polystyrene weight ratio of 1.0 exhibited superior catalytic activity, and under a higher gas hourly space velocity (GHSV) of 70000 h^–1, the 90% conversion of o-xylene has been obtained at around 200°C. The BET and SEM results indicated that Pd/MMSb catalyst possesses high surface area and large pore volume, and well-ordered, interconnected macropores and 2D hexagonally mesopores hybrid network. This novel ordered hierarchical porous structure was highly beneficial to the dispersion of active sites Pd nanoparticles with less aggregation, and facilitates diffusion of reactants and products. Furthermore, the Pd/MMS-b catalyst possessed good stability and durability.     

Nanomaterials for environmental burden reduction, waste treatment, and nonpoint source pollution control: a review

Nanomaterials are applicable in the areas of reduction of environmental burden, reduction/treatment of industrial and agricultural wastes, and nonpoint source (NPS) pollution control. First, environmental burden reduction involves green process and engineering, emissions control, desulfurization/denitrification of nonrenewable energy sources, and improvement of agriculture and food systems. Second, reduction/treatment of industrial and agricultural wastes involves converting wastes into products, groundwater remediation, adsorption, delaying photocatalysis, and nanomembranes. Third, NPS pollution control involves controlling water pollution. Nanomaterials alter physical properties on a nanoscale due to their high specific surface area to volume ratio. They are used as catalysts, adsorbents, membranes, and additives to increase activity and capability due to their high specific surface areas and nano-sized effects. Thus, nanomaterials are more effective at treating environmental wastes because they reduce the amount of material needed.     

汽车排气净化催化剂三效性能的研究

本文对Ky系列催化剂处理汽车排气中CO,HC和NO_x的三效性能进行了研究,用CVS法测定排放污染物的重量和转化效率;通过行车60 000km,证明高温老化引起催化剂表面结构的改变,是导致催化剂活性下降的主要原因,新改进的催化剂有较好的热稳定性和三效性能。     

ZrO2掺杂的V2O5/TiO2催化剂表征及催化还原NOx

采用共沉淀法制备出不同锆掺杂量的钛锆复合载体(TiO2-ZrO2),运用XRD和BET研究其微观结构,结果显示钛锆物质的量之比1∶1时复合载体具有最大的比表面积,可达256.01 m.2g-1.以此为载体制备了V2O5/TiO2-ZrO2催化剂,并添加少量CeO2对其改性.采用XRD、BET、H2-TPR、原位FT-IR等手段研究其活性组分的表面分散状态、氧化还原特性和表面酸性.结果显示,V2O5高度分散在载体上;与纯V2O5相比,复合载体上V2O5的还原峰向低温方向发生了偏移;催化剂表面包含了大量的B酸和L酸.模拟氨气催化还原NO(NH3-SCR)的脱硝反应活性测试表明,V2O5/TiO2-ZrO2催化剂具有较好的热稳定性和较宽的活性窗口,少量CeO2的加入提高了催化剂的低温活性.     

NiB2O4 (B = Mn or Co) catalysts for NH3-SCR of NOx at low-temperature in microwave field

● Microwave-assisted catalytic NH₃-SCR reaction over spinel oxides is carried out. ● SCR reaction temperature is tremendously lowered in microwave field. ● NO conversion of NiMn₂O₄ is highly up to 90.6% at 70°C under microwave heating. Microwave-assisted selective catalytic reduction of nitrogen oxides (NO_x) was investigated over Ni-based metal oxides. The NiMn₂O₄ and NiCo₂O₄ catalysts were synthesized by the co-precipitation method and their activities were evaluated as potential candidate catalysts for low-temperature NH₃-SCR in a microwave field. The physicochemical properties and structures of the catalysts were characterized by X-ray diffraction (XRD), Scanning electron microscope (SEM), N₂-physisorption, NO adsorption-desorption in the microwave field, H₂-temperature programmed reduction (H₂-TPR) and NH₃-temperature programmed desorption (NH₃-TPD). The results verified that microwave radiation reduced the reaction temperature required for NH₃-SCR compared to conventional heating, which needed less energy. For the NiMn₂O₄ catalyst, the catalytic efficiency exceeded 90% at 70 °C and reached 96.8% at 110 °C in the microwave field. Meanwhile, the NiMn₂O₄ also exhibited excellent low-temperature NH₃-SCR reaction performance under conventional heating conditions, which is due to the high BET specific surface area, more suitable redox property, good NO adsorption-desorption in the microwave field and rich acidic sites.     

稀土修饰的Co/Hβ催化剂催化分解N_2O

以Hβ分子筛为载体,采用浸渍法制备了一系列以钴为主活性组分,稀土元素为助剂的CoM/Hβ（M=La、Ce、Pr、Nd）催化剂,考察了在含氧条件下直接催化分解N2O的性能.采用X射线衍射、热重-质谱联用系统、H2-TPR、NH3-TPD等方法对催化剂进行了表征.XRD结果表明,Co物种主要以Co3O4尖晶石形态存在.NH3-TPD结果表明,催化剂活性与催化剂的酸性有关.活性评价结果显示,稀土助剂的添加使催化剂活性得到改善,其中以Pr为助剂的催化剂活性最好,N2O转化率达到95%时的反应温度为398℃.