Furfuryl alcohol functionalized graphene nanosheets for synthesis of high carbon yield novolak composites

Graphene oxide and furfuryl alcohol modified graphene nanosheets (G‐FA) were used to prepare graphene/novolak composites. Effect of graphene compatibilization on the properties of the composites especially carbon yield value is evaluated. Both types of graphene nanosheets were dispersed uniquely in the novolak matrix as proved by X‐ray diffraction analysis. However, modification of graphene sheets by furfuryl alcohol results in more improved dispersions. Thermogravimetric analysis confirms the elevated thermal stability of the nanocomposites in comparison with the neat novolak. In addition, G‐FA containing composites have higher carbon yield values. A shift in the wave number of characteristic bonds of graphene after oxidation and modification with furfuryl alcohol, O? H, C?O, and C? O bonds, are seen in the Fourier transform infrared spectroscopy spectra. Raman results and scanning electron microscopy images show that graphene nanosheets reduced in size and wrinkled by oxidation and functionalization. Transmission electron microscopy image of the composite with 0.2 wt % of G‐FA reveals the presence of nanosheets with curvature. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40273.     

复合床层变压吸附法脱除合成气中微量CO和CO_2

采用分别装载活性炭和NA型吸附剂的复合床层的变压吸附工艺来脱除合成气中微量的CO和CO2,并利用Aspen-Adsim软件对其进行模拟和优化。模拟结果表明,吹扫气量对工艺性能有较大的影响,吹扫气由处在顺放步骤的吸附塔提供,因此在顺放步骤将床层压力降至较低压力,可获得较大的吹扫气量,此时的工艺性能也较优。模拟结果还表明,均压次数对工艺性能也有影响。在相同的顺放压降下,将变压吸附过程中的3次均压变为2次均压,可减少吸附剂用量,吸附剂产率更高,但塔底尾气量要相应增加。     

Microwave-assisted synthesis of layered basic zinc acetate nanosheets and their thermal decomposition into nanocrystalline ZnO

We have developed a low-cost technique using a conventional microwave oven to grow layered basic zinc acetate (LBZA) nanosheets (NSs) from a zinc acetate, zinc nitrate and HMTA solution in only 2 min. The as-grown crystals and their pyrolytic decomposition into ZnO nanocrystalline NSs are characterized by scanning electron microscopy (SEM), energy-dispersive X-ray spectroscopy (EDS), atomic force microscopy (AFM), X-ray diffraction (XRD) and photoluminescence (PL). SEM and AFM measurements show that the LBZA NSs have typical lateral dimensions of 1 to 5 μm and thickness of 20 to 100 nm. Annealing in air from 200°C to 1,000°C results in the formation of ZnO nanocrystalline NSs, with a nanocrystallite size ranging from 16 nm at 200°C to 104 nm at 1,000°C, as determined by SEM. SEM shows evidence of sintering at 600°C. PL shows that the shape of the visible band is greatly affected by the annealing temperature and that the exciton band to defect band intensity ratio is maximum at 400°C and decreases by a factor of 15 after annealing at 600°C. The shape and thickness of the ZnO nanocrystalline NSs are the same as LBZA NSs. This structure provides a high surface-to-volume ratio of interconnected nanoparticles that is favorable for applications requiring high specific area and low resistivity such as gas sensing and dye-sensitized solar cells (DSCs). We show that resistive gas sensors fabricated with the ZnO NSs showed a response of 1.12 and 1.65 to 12.5 ppm and 200 ppm of CO at 350°C in dry air, respectively, and that DSCs also fabricated from the material had an overall efficiency of 1.3%.

PACS

81.07.-b; 62.23.Kn; 61.82.Fk     

Preferential CO oxidation over activated carbon supported catalysts in H2-rich gas streams containing CO2 and H2O

Selective CO oxidation (PROX) was studied at 423 K over 1% Pt–0.25% SnO_x and 1% Pt–1% CeO_x catalysts supported on un-oxidized and oxidized activated carbon (AC) using feed mixtures simulating the reformate coming from fuel processors. Effects of the addition of 15% CO₂ or (15% CO₂ + 10% H₂O) into feed mixtures containing 1% CO, 1% O₂, 60% H₂ and He were determined for nine different AC-supported catalysts, and the results were compared with those obtained with pure H₂-rich feed. Unlike other PROX catalysts having oxide supports, introduction of CO₂ into pure feed drastically increased CO conversion on all nine catalysts supported on oxidized or un-oxidized AC regardless of impregnation strategy.1% Pt–0.25% SnO_x supported on HNO₃-oxidized AC stands out as a potential candidate for commercial use in PROX since it yields 100% CO conversion under realistic feed conditions. 1% Pt–1% CeO_x catalysts prepared by sequential or co-impregnation and supported on air-oxidized AC also give 100% CO conversion in H₂-rich feed containing (CO₂ + H₂O) during extended run times and hence hold promise as PROX catalysts.     

Large-scale and controllable synthesis of metal-free nitrogen-doped carbon nanofibers and nanocoils over water-soluble Na2CO3

Using acetylene as carbon source, ammonia as nitrogen source, and Na₂CO₃ powder as catalyst, we synthesized nitrogen-doped carbon nanofibers (N-CNFs) and carbon nanocoils (N-CNCs) selectively at 450°C and 500°C, respectively. The water-soluble Na₂CO₃ is removed through simple washing with water and the nitrogen-doped carbon nanomaterials can be collected in high purity. The approach is simple, inexpensive, and environment-benign; it can be used for controlled production of N-CNFs or N-CNCs. We report the role of catalyst, the effect of pyrolysis temperature, and the photoluminescence properties of the as-harvested N-CNFs and N-CNCs.     

二维石墨相氮化碳纳米片的制备及其光催化性能

利用水热反应法将三聚氰胺悬浊液在200℃下反应生成中间产物,中间产物经煅烧直接制成了二维石墨相氮化碳(g-C3N4)纳米片(WCN),并与本体g-C3N4(CN)、传统热氧剥离法得到的g-C3N4纳米片(OCN)进行了比较.采用SEM、XRD、FTIR、Raman、AFM、PL对样品进行了表征,探讨了其光电化学性能和光催化性能.结果表明,两种方法均实现了对CN的剥离,WCN和OCN与CN的晶体结构和组成相同,WCN和OCN比表面积分别是CN的3.6倍和3.1倍.光电化学分析显示,WCN具有更好的载流子迁移与分离效率,具有较好的光催化活性.可见光照射下,WCN对亚甲基蓝(MB)的光催化降解率达到82.0％,分别是OCN和CN的2.4倍和6.7倍,光催化降解过程符合一级动力学方程.WCN具有优良的稳定性和可重复利用性能.     

二维石墨相氮化碳纳米片的制备及其光催化性能

摘要：利用水热反应法,将三聚氰胺悬浊液在200 ℃下反应生成中间产物,然后煅烧中间产物直接制成了二维石墨相氮化碳g-C3N4纳米片（WCN）,并与本体g-C3N4(CN)、传统热氧剥离法得到的g-C3N4纳米片（OCN）进行了比较。采用SEM、XRD、FTIR、Raman、AFM、PL仪等对催化剂进行了表征,探讨了催化剂的光电化学性能和光催化性能。结果表明：两种方法均实现了对CN的剥离,WCN和OCN二维纳米片与CN 晶体结构和组成相同,WCN和OCN的比表面积分别是CN的4倍和3倍。光电化学分析显示WCN有更好的载流子的迁移与分离效率,具有较好的光催化活性。在可见光条件下,WCN对亚甲基蓝（MB）的光催化降解率达到82％,分别是OCN和CN的2.4 倍和6.7 倍,光催化降解过程符合一级动力学方程。WCN具有优良的稳定性和可重复利用性能。     

Experimental study on capturing CO 2 greenhouse gas by mixture of ammonia and soil

This paper presents our study on removal of carbon dioxide (CO₂) greenhouse gas emissions by using the mixture of ammonia and soil. CO₂ capture capacity using this method is 15% higher than the sum of ammonia chemical absorption capacity and soil physical adsorption capacity. Scanning electron microscopy (SEM) and Fourier transform infrared spectroscopy (FTIR) are utilized to study this synergism. The removal effect is not only reflected in ammonia chemical reaction with CO₂. CO₂ can also be absorbed by ammonium bicarbonate (NH₄HCO₃) crystal, which is the main component of the product, or wrapped in the pore of the crystal or packed in the gap between the crystal and the soil. CO₂ can be permanently deposited as carbonated minerals in the subsoil earth layers.     

CO2, N2 gas sorption and permeation behavior of chitosan membrane

The sorption equilibria for CO₂ and N₂ in dry chitosan membrane at 20 and 30 ‡C were measured by a pressure decay method. The steady-state permeation rates for CO₂ and N₂ in dry and wet (swollen with water vapor) chitosan membranes at 20 and 30 ‡C were measured by a variable volume method. The sorption equilibrium for N₂ obeyed Henry’s law, whereas that for CO₂ was described apparently by a dual-mode sorption model. This non-linear sorption equilibrium for CO₂ could be interpreted by the interaction of sorbed CO₂ with the chitosan matrix expressed as a reversible reaction. The logarithm of the mean permeability coefficient for CO₂ in dry chitosan membrane increased linearly with upstream gas pressure. A linear increase of the logarithmic mean permeability coefficient for CO₂ with the pressure could be interpreted in terms of a modified free-volume model. The mean per-meability coefficient for N₂ in dry chitosan membrane only slightly increased with upstream gas pressure. The per-meabilities for CO₂ and N₂ in wet chitosan membrane increased by 15 to 17 times and 11 to 15 times, respectively, as compared to those in the dry membrane.     

Exclusion of CO and CO2 from ammonia synthesis gas by an electrocatalytic process

A new exclusion process for CO and CO₂ from ammonia synthesis gas has been proposed: this takes place at room temperature and atmospheric pressure. The process is based on the electrochemical reduction of CO and CO₂ to methanol proceeding at a mediated electrode via homogeneous catalysis. The maximum percentages of CO and CO₂ excluded from the initial gas were about 1.5 and 4.1%, respectively, with a mediated electrode of 82.8 cm² area in a reaction time of 5 h. The amount of excluded CO and CO₂ was equivalent to the sum of moles of methanol formed and gases dissolved into the solution alone. The electroreduction of CO and CO₂ was more efficient at three-phase (electrode/solution/gas) and at two-phase (electrode/solution) interfaces, respectively.     

Potassium salt-assisted synthesis of highly microporous carbon spheres for CO2 adsorption

Highly microporous carbon spheres for CO₂ adsorption were prepared by using a slightly modified one-pot Stöber synthesis in the presence of potassium oxalate. Formaldehyde and resorcinol were used as carbon precursors, ammonia as a catalyst, and potassium oxalate as an activating agent. The resulting potassium salt-containing phenolic resin spheres were simultaneously carbonized and activated at 800 °C in flowing nitrogen. Carbonization of the aforementioned polymeric spheres was accompanied by their activation, which resulted in almost five-time higher specific surface area and total pore volume, and almost four-time higher micropore volume as compared to analogous properties of the carbon sample prepared without the salt. The proposed synthesis resulted in microporous carbon spheres having the surface area of 2130 m² g⁻¹, total pore volume of 1.10 cm³ g⁻¹, and the micropore volume of 0.78 cm³ g⁻¹, and led to the substantial enlargement of microporosity in these spheres, especially in relation to fine micropores (pores below 1 nm), which enhance CO₂ adsorption. These carbon spheres showed three-time higher volume of fine micropores, which resulted in the CO₂ adsorption of 6.6 mmol g⁻¹ at 0 °C and 1 atm.     

Promotion through gas phase induced surface segregation: methanol synthesis from CO, CO2 and H2 over Ni/Cu(100)

We have studied the rate of methanol formation over Cu(100) and Ni/Cu(100) from various mixtures of CO, CO₂ and H₂. It is found that the presence of submonolayer quantities of Ni leads to a strong increase in the rate of methanol formation from mixtures containing all three components whereas Ni does not influence the rate from mixtures of CO₂/H₂ and CO/H₂, respectively. The influence of the partial pressures of CO and CO₂ on the rate indicates that the role of CO is strictly promoting. From temperature-programmed desorption spectra it follows that the surface concentration of Ni depends strongly on the partial pressure of CO. In this way the increase in reactivity is interpreted as a CO-induced structural promotion introduced by the stronger bonding of CO to Ni as compared to Cu. It is suggested that this type of promotional behavior will be of general importance in existent catalysts and perhaps even more relevant in the development of new or improved bimetallic catalysts. This revised version was published online in July 2006 with corrections to the Cover Date.     

Optimization-based identification of CO2 capture and utilization processing paths for life cycle greenhouse gas reduction and economic benefits

This paper introduces a mathematical formulation to identify promising CO₂ capture and utilization (CCU) processing paths and assess their production rates by solving an optimization problem. The problem is cast as a multi-objective one by simultaneously maximizing a net profit and life cycle greenhouse gas (GHG) reduction. Three case studies are illustrated using an exemplary CCU processing network. The results indicate the optimal solution is greatly influenced by the scale of CO₂ emission source, market demand, and hydrogen availability. Moreover, with the current system of measuring the GHG reduction regarding a business-as-usual level, if the aim is to achieve a GHG reduction within a national boundary, the question of whether CCU plants producing a product of same functionality through conventional means, which the CO₂-based product can replace, exists in the country can come into consideration. This systematic identification will assist decision-making regarding future R&D investment and construction of large-scale CCU plants.     

改性蜂窝状活性炭吸附二氧化碳和氮气的热力学

蜂窝状活性炭具有较高的比表面积、多孔道、压降低、吸脱附速率快、不易堵塞等优点,因此被认为是捕集烟道气中CO₂重要吸附材料。选用蜂窝状煤基和椰壳两种活性炭吸附剂,采用磁悬浮热天平分别测定了CO₂和N₂的吸附等温线。采用1 mol·L^-1 K₂CO₃对蜂窝状活性炭材料进行浸渍改性,提高在低二氧化碳分压下的CO₂吸附性能。采用Langmuir、multi-site Langmuir和Virial 3种模型对吸附平衡数据进行拟合,得出热力学参数,为后续吸附工艺优化设计提供基础数据。结果表明在实验范围内3种模型均能对实验测量的等温线进行较好的拟合,Langmuir模型总体拟合效果最好。     

A low-cost and efficient pathway for preparation of 2D MoN nanosheets via Na2CO3-assisted nitridation of MoS2 with NH3

In this paper, an efficient and low-cost method was developed for producing isolated 2D MoN nanosheets via Na₂CO₃-assisted nitridation and exfoliation of natural 2H-MoS₂ by NH₃ at 700-800°C. It was found that, in the presence of Na₂CO₃, the nitridation of MoS₂ with NH₃ was a topochemical transformation. After heat treatment the mixture of MoS₂ and Na₂CO₃ in NH₃ at 700-800°C, layered MoN with intercalated Na₂S was obtained. Na₂CO₃ can dramatically promote the topochemical nitridation and exfoliation of MoS₂ in NH₃. At 750°C, the time for complete nitridation of (commercial) MoS₂ can be shortened to 2 hours, which is much shorter than 40 hours in the case without the addition of Na₂CO₃ as reported in the previous literature. After acid-washing, the intercalated Na₂S was removed, and the generated H₂S promoted the further separation of the MoN nanosheets. Finally, dispersed high crystalline 2D MoN nanosheets with thickness of a few nanometers were successfully produced. This method may be also applicable for the production of other 2D nitrides or carbides by nitridation or carbonization of various transition metal dichalcogenides (TMDs) with the assistance of sulfur-fixed agent.     

二氧化碳再生乙酸乙烯合成用触媒载体活性炭

提出用二氧化碳活化法再生乙酸乙烯合成用触媒载体活性炭工艺。研究了活化温度、活化时间和二氧化碳流量对活性炭吸附性能和得率的影响。确定最佳工艺条件为活化温度1 273 K,活化时间100 m in,二氧化碳流量0.5 L/m in,在此条件下得到的活性炭碘吸附值为1 091.33 mg/g,乙酸吸附值为518.30 mg/g,强度为72%,活化得率为80.33%,并对制得的活性炭做了比表面积测定和孔结构分析。再生后的活性炭强度和乙酸吸附值均达到标准,符合乙酸乙烯合成用触媒载体活性炭的要求。     

气相色谱法分析合成苯乙酸用CO气体

介绍有关气相色谱法对合成苯乙酸用CO气体的分析测试,探讨了减小该测定误差的方法。     

功能化离子液体用于CO2吸收和分离的研究进展

离子液体的结构具有高度可调性,可通过改变阴阳离子的结构改变其物理、化学性能,实现离子液体的功能化。功能化离子液体可用于分离、电化学、催化剂、有机合成等方面,已成为离子液体领域的研究热点。本文综述了含氟、含氨基和其它极性基团的功能化离子液体吸收CO₂的研究进展,介绍了功能化离子液体支撑液膜分离CO₂的研究,指出了今后研究需解决的问题。     

Nanocrystalline Zeolite Tetraethylammonium‐Beta Membrane for Preferential Sorption and Transport of CO2 over N2

CO₂/N₂ gas separation was performed over a nanocrystalline zeolite tetraethylammonium (TEA)‐beta membrane prepared on a stainless‐steel porous disc by repeated hydrothermal crystallization. Two to three consecutive hydrothermal syntheses were required to form a membrane comprised of a continuous and compact layer of zeolite beta nanocrystals on the support. The membrane TEA‐BEA3 obtained by three consecutive syntheses, in which the membrane from two consecutive syntheses was used as support, exhibited the highest structural order. When the separation experiment was performed over this membrane without applying any external applied pressure, 100 % selectivity of CO₂ over N₂ was observed. The separation was driven by differences in chemical potentials of the molecules generated only by the adsorption‐desorption behavior of the gases into the membrane. The novel zeolite TEA‐beta membrane provided promising results for the separation of small gas molecules due to the combined influence of diffusion and sorption selectivity.