Experimental evidence for the formation mechanism of metallic catalyst-free carbon nanotubes

Our work reported that the so-called pure carbon nanotubes(CNTs)can be synthesized without metallic catalyst by chemical vapor deposition(CVD).The as-prepared CNTs have average diameter of 50 nm and length over several microns.Analysis of intermediate objects in the products indicates that their formation mechanism follows the wire-to-tube model.Besides,according to thermodynamic analysis of the driving force combing with experimental results,we find that the thermal gradient can effectively favor the formation of CNTs in our metallic catalyst-free CVD.

Characterization of free carbon in the as-thermolyzed Si-B-C-N ceramic from a polyorganoborosilazane precursor

Polyorganoborosilazane((B[C_(2)H_(4)-Si(CH_(3))NH]_(3))n)was synthesized via monomer route from a single-source precursor and thermolyzed at 1300℃in argon atmosphere.The as-thermolyzed Si-B-C-N ceramic was characterized using X-ray diffraction(XRD)and Raman spectroscopy.The crystallization behavior of silicon carbide in the as-thermolyzed amorphous Si-B-C-N matrix was understood by XRD studies,and the crystallite size calculated using Scherrer equation was found to increase from 2 nm to 8 nm with increase in dwelling time.Concomitantly,Raman spectroscopy was used to characterize the free carbon present in the as-thermolyzed ceramic.The peak positions,intensities and full width at half maximum(FWHM)of D and G bands in the Raman spectra were used to study and understand the structural disorder of the free carbon.The G peak shift towards 1600 cm-1 indicated the decrease in cluster size of the free carbon.The cluster diameter of the free carbon calculated using TK(Tuinstra and Koenl)equation was found to decrease from 6.2 nm to 5.4 nm with increase in dwelling time,indicating increase in structural disorder.

Rational design of carbon-based metal-free catalysts for electrochemical carbon dioxide reduction: A review

Electrochemical CO2 reduction to chemicals or fuels presents one of the most promising strategies for managing the global carbon balance, which yet poses a significant challenge due to lack of efficient and durable electrocatalyst as well as the understanding of the CO2 reduction reaction(CO2RR) mechanism.Benefiting from the large surface area, high electrical conductivity, and tunable structure, carbon-based metal-free materials(CMs) have been extensively studied as cost-effective electrocatalysts for CO2RR.The development of CMs with low cost, high activity and durability for CO2RR has been considered as one of the most active and competitive directions in electrochemistry and material science.In this review article,some up-to-date strategies in improving the CO2RR performance on CMs are summarized.Specifically, the approaches to optimize the adsorption of CO2RR intermediates, such as tuning the physical and electronic structure are introduced, which can enhance the electrocatalytic activity of CMs effectively.Finally, some design strategies are proposed to prepare CMs with high activity and selectivity for CO2RR.

Grain size characteristics of the carbonate-free fraction of surface sediments from the Southwest Indian Ridge area and its geological significance

The carbonate-free fraction of 20 surface sediments collected from the ultraslow-spreading Southwest Indian Ridge(SWIR) was studied by grain size analysis and mineralogical analysis with X-ray powder diffraction(XRD),stereo microscopy and scanning electron microscopy(SEM). The characteristics of the carbonate-free fraction of the sediments were obtained, and related influential factors were discussed. The results show that the mean grain size of this fraction is in 1.96Φ–8.19Φ, with poorly sorting and unimodal, bimodal or irregular bimodal distribution patterns. Four grain size end members of the fraction are derived with the End Member Model method. The finest end member EM1 shows a significant contribution of terrigenous materials of the aeolian input and sediment carried by the bottom current. End member EM2 with medium size mainly reflects sediment of a siliceous bioclast origin. EM3 and EM4 are interpreted as representing the coarser volcanic materials related to bedrock weathering or volcanic activities. Multi-provenance is the dominant factor controlling the grain size pattern of the carbonate-free fraction of the sediments in that area. In addition, sediment transport processes such as the bottom current and wind are the minor factors that influence the grain size distribution of the carbonate-free fraction sediments.

Free Radicals in Organic Matter for Thermal History Reconstruction of Carbonate Succession

Geothermometer is one of the most useful methods to reconstruct the thermal history of sedimentary basins. This paper introduces the application of free radicals concentration of organic matter as a thermal indicator in the thermal history reconstruction of carbonate succession, based on anhydrous thermal simulation results of type I and H1 kerogen. A series of free radicals data are obtained under thermal simulation of different heating temperatures and times, and quantitative modds between free radical concentration （Ng） of organic matter and time-temperature index （TTI） for types I and type H1 kerogen are also obtained. This Ng.TTI relation was used to model the Ordovician thermal gradients of Well TZ12 in the Tarim Basin. The modeling result is corresponding to the results obtained by apatite fission track data and published data. This new method of thermal history reconstruction will be benefit to the hydrocarbon generation and accumulation study and resource assessment of carbonate succession.

Millimeter-Wave Absorption Properties of Thin Wave Absorber in Free Space with New Porous Carbon Material

In this paper, we focus on PHYTOPOROUS, a porous carbon material made entirely from plant-based ingredients, as a new broadband-wave absorber material that acts in the millimeter wave band. We created prototypes of thin rubber-sheet wave absorbers that contain porous carbon (PHYTOPOROUS) made from rice chaff and soybean hulls, which are both agricultural residue products that are generated in large quantities. We investigated the permittivity and reflectance characteristics of this material using the free-space time-domain method. The thin rubber-sheet wave absorber that contained PHYTOPOROUS made from soybean hulls exhibited a frequency band that was approximately 18 GHz wide and centered at 90 GHz. The return loss for this material was greater than −20 dB. This demonstrates that the material provides nearly constant reflection absorption over a wide frequency band.

Ultrahigh rate binder-free Na_3V_2(PO_4)_3/carbon cathode for sodium-ion battery

Sodium ion batteries （SIBs） are very promising for large-scale energy storage in virtue of its high energy density, abundant sodium resources and low environmental impact, etc. However, it is still a big chal- lenge to develop high-performance and durable cathode materials for SIBs. Among different candidate materials, Na_3V_2（PO_4）_3 has attracted great attentions due to its high theoretical capacity （117 mAh/g）, stable framework structure and excellent ionic conductivity. However, Na_3V_2（PO_4）_3 delivers inferior rate capability and cycling stability due to its poor electronic conductivity. In this work, free-standing Na_3V_2（PO_4）_3/carbon nanofiber membranes are synthesized by an electrospinning-sintering mute. The sample could deliver excellent cycling capability with specific capacity of 112 mAh/g at 1 C after 250 cycles and ultrahigh rate capability with 76.9 mAh/g even at 100 C, which is superior to many state-of- the-art SIB cathode materials. This can be attributed to the hierarchically distributed Na_3V_2（PO_4）_3 crystals in carbon nanofiber network, which possesses outstanding electronicfionic conductivity and thus leads to an ultrahigh rate capabilitY.

Liver Nuclear Activation of Carbon Tetrachloride or Bromotrichloromethane to Trichloromethyl and Trichloromethylperoxyl Free Radicals.Their Reactions With Lipids and Proteins

The formation of·CCl3 radicals in liver nuclei was suggested by spin trapping of them with N-t-butyl-α-phenylnitrone followed by GC/MS detection of the resulting adduct. Comparison of its formation in microsomal biotransformation of CCl4 was made. In aerobic nuclear activation mixtures containing NADPH and CCl4, significant decrease in the arachidonic acid content of nuclear lipids was observed (27. 8%, compared to control), the intensity of this decrease was lower than that occurring in the corresponding microsomal incubation mixtures (29.1%). Significant decreases in arachidonic acid content of nuclear and endoplasmic reticulum lipids were also observed in animals at 6 hours of poisoning with the haloalkane. During aerobic nuclear metabolism of CCl4 or CBrCl3, cholesterol oxidation products were detected: a ketocholesterol, an epoxide like structure and 7-ketocholesterol. Nuclear protein carbonyl formation was not promoted during nuclear CCl4 biotransformation. NADPH by itself may lead to protein carbonyl formation during prolonged periods of incubation. CBrCl3 in contrast, led to decreased protein carbonyl formation. No increase in nuclear protein carbonyl formation was observed in CCl4 intoxicated animals during periods of time between 1 to 6 hours after treatment. The results indicate that during nuclear biotransformation of CCl4 or CBrCl3 reactive free radicals, PUFA degradation, reactive aldehydes and cholesterol oxidation products are formed, nearby DNA and regulatory proteins.

Research on Properties of Metasilicate Bonded Carbon-free Basic Dry Vibration Mix

Carbon-free basic dry vibration mix was prepared using middle grade magnesia and fused magnesia as main starting materials,metasilicate replacing phenolic resin as binder,adding a certain amount of medium and low temperature intensifiers. Effects of binder,grain composition,and additives on basic dry vibration mix for tundish were studied,and the bonding mechanism was also analyzed. The results show that：（1） when using metasilicate as binder,the higher strength can be acquired; （2） the suitable grain composition is q=0.48,the critical granularity is 5 or 3 mm,the fines addition is 10%-20% （mass percent）; （3） the strength and corrosion resistance of the basic dry vibration mix can be improved by the melting compound of metasilicate and additives; （4） with temperature rising,the bonding type in dry vibration mix changes from cohere bonding to reaction bonding,and then to ceramic bonding at last.

Development and application of fluorine-free mold powder for low carbon steel

Fluorine in mold powder is known as harmful to human health and the environment. Being the advocate of green production, Baosteel developed an environmentally friendly mold powder without fluorine. The main problem of fluorine-free flux film is small heat resistance and thus the heat transfer intensity of the mold is too large, which to some extent hinders the increase of the casting speed. With the heat flow simulation equipment, controlling precipitation of crystal in flux and solidification temperature properly, fluorine-free mold powder for low carbon steel,which substitutes F with B203 ,was successfully developed and applied in industrial production. The production results show that, by using boronic fluorine-free mold powder,the boron increment in molten steel is less than 1.3ppm for conventional aluminium killed low carbon steel.

High-performance doping-free carbon-nanotube-based CMOS devices and integrated circuits

Ballistic n-type carbon nanotube(CNT)-based field-effect transistors(FETs) have been fabricated by contacting semiconducting single-walled CNTs(SWCNTs) using Sc or Y.The n-type CNT FETs were pushed to their performance limits through further optimizing their gate structure and insulator.The CNT FETs outperformed n-type Si metal-oxide-semiconductor(MOS) FETs with the same gate length and displayed better downscaling behavior than the Si MOS FETs.Together with the demonstration of ballistic p-type CNT FETs using Pd contacts,this technological advance is a step toward the doping-free fabrication of CNT-based ballistic complementary metal-oxide-semiconductor(CMOS) devices and integrated circuits.Taking full advantage of the perfectly symmetric band structure of the semiconductor SWCNT,a perfect SWCNT-based CMOS inverter was demonstrated,which had a voltage gain of over 160.Two adjacent n-and p-type FETs fabricated on the same SWCNT with a self-aligned top-gate realized high field mobility simultaneously for electrons(3000 cm2 V-1 s-1) and holes(3300 cm2 V-1 s-1).The CNT FETs also had excellent potential for high-frequency applications,such as a high-performance frequency doubler.

Probing the intrinsic catalytic activity of carbon nanotubes for the metal-free oxidation of aromatic thiophene compounds in ionic liquids

A metal-free catalytic system combining oxidized carbon nanotubes (oCNTs) and ionic liquids (ILs) is presented for the oxidation of aromatic thiophene compounds with H2O2 as an oxidant. The oCNTs exhibit impressively high activity and stability in the system, which show an even better performance than those of some reported metal catalysts. The ILs are proved to have indispensable influence on the enhanced catalytic performance of the oCNTs. Detailed characterization by TG-MS and XPS demonstrates that the carbonyl groups are the active sites for the oxidation process, which is further supported by the deactivation and the model catalysts experiments. The quantitative analysis of different oxygen groups in oCNTs could be achieved by an isothermal temperature programmed TG-MS method. The concentration of carbonyl groups is 1.46 mmol per 1 g oCNTs and the tuiriover frequency of oCNTs could also be obtained (10.7 h^-1 in the presence of OmimPF6). H2O2 decomposition experiments combined with the EPR results reveal that the presence of OmimPF6 can avoid the intermediate HO· to form O2 and then improve the catalytic performance of oCNTs for the oxidation of dibenzothiophene.

N, F?Codoped Microporous Carbon Nanofibers as Efficient Metal?Free Electrocatalysts for ORR

Currently, the oxygen reduction reaction(ORR) mainly depends on precious metal platinum(Pt) catalysts. However, Pt-based catalysts have several shortcomings, such as high cost, scarcity, and poor long-term stability. Therefore, development of e cient metal-free electrocatalysts to replace Pt-based electrocatalysts is important. In this study, we successfully prepared nitrogen-and fluorinecodoped microporous carbon nanofibers(N, F-MCFs) via electrospinning polyacrylonitrile/polyvinylidene fluoride/polyvinylpyrrolidone(PAN/PVDF/PVP) tricomponent polymers followed by a hydrothermal process and thermal treatment, which was achieved for the first time in the literature. The results indicated that N, F-MCFs exhibit a high catalytic activity(E_(onset): 0.94 V vs. RHE, E_(1/2): 0.81 V vs. RHE, and electron transfer number: 4.0) and considerably better stability and methanol tolerance for ORR in alkaline solutions as compared to commercial Pt/carbon(Pt/C, 20 wt%) catalysts. Furthermore, in acidic media, N, F-MCFs showed a four-electron transfer pathway for ORR. This study provides a new strategy for in situ synthesis of N, F-MCFs as highly e cient metal-free electrocatalysts for ORR in fuel cells.

Doping-free carbon nanotube optoelectronic devices

Semiconducting carbon nanotubes(CNTs) possess outstanding electrical and optical properties because of their special one-dimen-sional(1D) structure.CNTs are direct bandgap materials,which makes them ideal for use in optoelectronic devices,e.g.light emitters and light detectors.Excitons determine their light absorption and light emission processes due to the strong Coulomb interactions between electrons and holes in CNTs.In this paper,we review recent progress in CNT photodetectors,photovoltaic devices and light emitters.In particular,we focus on the doping-free CNT optoelectronic devices developed by our group in recent years.

Wet carbon-based solid acid/NaNO_3 as a mild and efficient reagent for nitration of aromatic compound under solvent free conditions

Nitro aromatic compound can be obtained in high yields via nitration of aromatic compound with wet carbon-based solid acid and NaNO_3 under solvent free oxidation at room temperature.

Glycerol-Based Carbon-SO₃H Catalyzed Benign Synthetic Protocol for the Acetylation of Alcohols, Phenols and Amines under Solvent-Free Conditions

A simple and efficient solvent-free method was developed for the acetylation of alcohols, phenols and amines in excellent yields employing glycerol-based sulfonic acid (-SO3H) functionalized carbon catalyst under environmentally benign reaction conditions. The salient features of this protocol are the short reaction time, ease of product isolation and reusability of the carbon catalyst.

基于Aspen Plus的甲烷联合重整制合成气过程热力学计算

甲烷联合重整产物合成气的组成受热力学平衡控制,反应中积炭反应也受操作条件的影响,因此,计算反应条件(原料组成、温度、压力)对产物组成和积炭形成的影响,进行定量热力学分析是工艺设计所需要的。本文使用Aspen Plus软件中的RGibbs模块,建立甲烷联合重整热力学反应模型,采用吉布斯自由能最小化法,考虑所有相关反应的进料组成、温度和压力对平衡反应混合物组成和积炭的影响。首先,设定化学计量比CH_(4)∶(CO_(2)+H_(2)O)=1∶1进料,调控CO_(2)、H_(2)O相对进料比例,结果发现:CO_(2)/CH_(4)比增加时,CH_(4)和CO_(2)转化率升高,但积炭量也相应增加,H_(2)/CO比减小;CH_(4)和CO_(2)的平衡转化率随温度升高而升高,且随着温度升高趋于极限,可通过调节温度从而调控H_(2)/CO比达到所需生产要求。然后,研究了压力对反应平衡的影响,结果表明CH_(4)和CO_(2)的热力学平衡转化率随压力升高而降低,积炭量增加。最后,结合进料比、温度和压力的影响,针对合成气制下游化学产品的不同需求以及特定氢碳比精准调控,模拟计算出合适的反应进料比例,为将来实际生产调控提供了理论计算依据。

碳源对反应烧结碳化硅性能的影响

以炭黑和石墨为碳源,控制碳添加量为10%(质量分数,下同),研究了不同炭黑、石墨比例对反应烧结碳化硅性能的影响。结果表明,当炭黑添加量为4%、石墨添加量为6%时,反应烧结碳化硅的力学性能较佳,此时抗弯强度为251.7 MPa,断裂韧性为4.29 MPa·m^(1/2)。通过XRD检测及对XRD谱进行Rietveld精修,分析发现炭黑添加量为4%、石墨添加量为6%的反应烧结碳化硅中的游离Si含量为24.44%(质量分数),而石墨添加量为10%的反应烧结碳化硅中的游离Si含量为28.57%(质量分数),相比前者游离Si含量较高,减少游离Si的含量可以提高反应烧结碳化硅的力学性能。

Zr-MOF固载聚离子液体对CO_(2)环加成反应的催化性能

通过无溶剂限域封装,将二溴对二甲苯和4,4′-联吡啶吸附至UiO-67材料微孔中,并原位聚合成聚离子液体PBpy-Br,得到兼具Br^(-),Zr-OH/Zr-OH_(2)和N杂环3种活性中心的复合材料PBpy-Br@UiO-67.采用X射线衍射(XRD)、傅里叶变换红外光谱(FTIR)、扫描电子显微镜(SEM)、^(13)C核磁共振波谱(^(13)C NMR)、比表面积分析(BET)和热重分析(TGA)等手段对材料进行了表征,并将其应用于催化CO_(2)与环氧氯丙烷的环加成反应中.在单因素实验基础上,通过响应面优化确定的最佳反应条件为反应温度100℃、p_(CO_(2))=0.1 MPa、催化剂用量(质量分数)0.22%以及反应时间22 h.在该条件下,环氧氯丙烷转化率达99.6%,催化剂循环使用5次后,转化率仅下降2.3%.此外,对PBpy-Br@UiO-67的普适性进行了研究,将其用于催化其它环氧化物与CO_(2)反应,转化率均在50%以上.研究结果表明,PBpy-Br@UiO-67催化剂具有反应条件温和及催化效率高的特点,为CO_(2)的固定与转化提供了新催化体系.

干酪根与芳烃化合物固—液有机质相互作用机理研究

地质条件下,烃源岩中最初生成的油气,达到饱和后,才能排出运移,而干酪根对烃类的吸附作用,是影响含油饱和度的重要因素。热解作用产生的烃类物质会与干酪根大分子发生相互作用,研究固体干酪根有机质对液态烃的溶解和吸附能力,可以明确烃源岩对烃类化合物的选择性滞留及生排烃特征。芳烃是石油烃类化合物的重要组成部分,在干酪根三维模型的基础上,利用Autodock软件将不同类型的芳烃化合物分子(包括苯、稠环芳烃和稠环芳烃衍生物)与不同成熟度的干酪根分子进行半柔性对接结算,计算两者结合所需的吉布斯自由能,研究芳烃化合物与干酪根结合的特征,从分子层面上研究干酪根吸附芳烃化合物的机理,揭示固—液有机质相互作用的本质。当与相同成熟度的干酪根结合时,稠环芳烃的分子质量越大、化合物中的甲基数量越多、分子缩合度越高,与干酪根分子结合所需的吉布斯自由能越低;芳烃化合物与干酪根分子之间相互作用受到芳烃的分子质量、分子缩合程度以及体系内甲基数量3个因素的影响。处于生烃高峰后,芳碳甲基含量较高的干酪根对芳烃的吸附能力较强;分子质量大、缩合度高的稠环芳烃及其衍生物与干酪根的结合能力较强;常规连接的小分子芳烃化合物在干酪根中的滞留能力较弱,更易发生排烃作用,运移富集成藏。