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.

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.

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.

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.

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.

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.

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.

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.

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.

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.

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.

Purified oxygenand nitrogen-modified multi-walled carbon nanotubes as metal-free catalysts for selective olefin hydrogenation

Oxygen and nitrogen-functionalized carbon nanotubes （OCNTs and NCNTs） were applied as metal-free catalysts in selective olefin hydro- genation. A series of NCNTs was synthesized by NH3 post-treatment of OCNTs. Temperature-programmed desorption, N2 physisorption, Raman spectroscopy, high-resolution transmission electron microscopy and X-ray photoelectron spectroscopy were employed to characterize the surface properties of OCNTs and NCNTs, aiming at a detailed analysis of the type and amount of oxygen- and nitrogen-containing groups as well as surface defects. The gas-phase treatments applied for oxygen and nitrogen functionalization at elevated temperatures up to 600 ℃ led to the increase of surface defects, but did not cause structural damages in the bulk. NCNTs showed a clearly higher activity than the pristine CNTs and OCNTs in the hydrogenation of 1,5-cyclooctadiene, and also the selectivity to cyclooctene was higher. The favorable catalytic properties are ascribed to the nitrogen-containing surface functional groups as well as surface defects related to nitrogen species. In contrast, oxygen-containing surface groups and the surface defects caused by oxygen species did not show clear contribution to the hydrogenation catalysis.

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。

打卡“长征”路线的无碳小车结构及轨迹仿真设计

根据2022年中国大学生工程实践与创新能力大赛要求,设计并制作了一台能打卡指定轨迹点(模拟长征路线)的自走式势能驱动车。运用SolidWorks的贝塞尔曲线,绘制经过特定轨迹点的拟合曲线;利用Matlab对拟合曲线进一步优化与仿真,从而获得满足设计要求的凸轮轮廓;创新运用SolidWorks逆向建模方法,设计弧面凸轮转向机构,配合激光打点微调机构,以提高小车运行轨迹精度和重复性;利用SoildWorks建立无碳小车的三维模型并对其结构进行了分析。小车运行结果表明,小车行走轨迹重复性好,能打卡指定的所有轨迹点。

集成有CNTs和Ni-Ni(OH)_(2)异质结构的电解析氢自支撑薄膜催化剂

氢气是一种重要的能量储存载体.通过电解水析氢的方式,可以将其他可再生能源转化为电能,并以化学能的形式储存于氢气中.为了提高电解析氢过程的能量转化效率、降低能耗,需要高活性的析氢催化剂.这些催化剂不仅应具有巨大的比表面积,还应具备适中的氢吸附能和较强的解离水的能力.铂基催化剂在电解析氢方面展现出了显著的优势,而同族的镍基催化剂因其高性价比而备受关注.然而,在电解析氢过程中,镍基催化剂存在氢吸附强度高和解离水能力弱两个重要缺陷,这导致析氢过程动力学不理想.因此,本文的研究思路是探索如何在镍基催化剂中引入功能性组分,以平衡氢吸附能和催化水解离的能力,从而实现析氢性能的提升.研究表明,碳纳米管(CNTs)可以改善催化剂的电解析氢性能,而Ni(OH)_(2)则可以提升催化剂解离水的能力.因此,本文采用复合电沉积法制得CNTs-Ni薄膜,并通过原位氧化在其表面形成Ni-Ni(OH)_(2)异质结构,构建了包含CNTs和Ni-Ni(OH)_(2)两种功能组分的CNTs-Ni-Ni(OH)_(2)薄膜.该薄膜展现出与Pt/C相当的析氢活性和更出色的稳定性.微观形貌分析显示,CNTs的引入使CNTs-Ni薄膜具有复杂的三维结构,镍以高度褶皱的微球形态均匀负载在CNTs表面,形成巨大的比表面积.电化学测试和模拟计算结果证实,CNTs-Ni薄膜的析氢活性较纯镍有显著提高,这归因于其巨大的电化学活性面积以及CNTs对析氢过程动力学的积极影响.当优化沉积时间和CNTs表面镍的负载量时,CNTs-Ni薄膜的电化学活性面积和析氢活性均得到显著提升.进一步氧化处理后,通过X射线光电子能谱和X射线衍射等测试手段证实了Ni-Ni(OH)_(2)异质结构的形成,并观察到电化学活性面积的增大和析氢活性的改善.此外,深入研究发现,随着氧化时间的延长,单位电化学活性面积上的析氢活性出现下降.结合析氢过程的背景电流分析推测,在析氢过程中CNTs-Ni-Ni(OH)_(2)表面发生氢氧化镍的还原,重新生成的镍活性位点对提升析氢过程动力学起到关键作用.但过长的氧化时间可能会破坏镍活性位点的再生.基于此理论构建的计算模型验证了CNTs和异质结构对析氢活性的协同增强作用,使氢的吸附自由能达到理想值,理论上氢在复合薄膜表面的析出过电位接近于0 V.因此,在碱性溶液中,集成有CNTs和Ni-Ni(OH)_(2)异质结构的CNTs-Ni-Ni(OH)_(2)析氢催化剂表现出优异的性能,其氢气起始析出电位为0 V,当阴极电流密度分别为10和50 mA/cm^(2)时,析氢过电位也仅为65和109 mV.综上所述,本文通过复合电沉积和原位氧化的方式获得了CNTs-Ni-Ni(OH)_(2)自支撑析氢催化剂,不仅体现出明显的几何效应,而且也对析氢过程的动力学产生了积极影响.这种整合多种功能性组分的方式,为未来设计和制备高活性、高性价比的电解析氢材料提供了新的思路.

一种无碳氮化硼前驱体的合成

以三氯化硼、二甲胺和氨气为原料,通过两步反应制得无碳六方氮化硼前驱体三胺基环硼氮烷及其聚合物,通过FTIR、~1HNMR对此无碳前驱体进行表征。将三胺基环硼氮烷及其聚合物在氮气气氛下烧结,制得六方氮化硼晶体,通过FTIR、XRD、SEM对六方氮化硼的结构进行表征。结果表明:以三胺基环硼氮烷及其聚合物为前驱体在氮气气氛下加热至1600℃,烧结6 h,得到不含碳且结晶度较好的六方氮化硼晶体,进一步表明前驱体为无碳前驱体。

新型环保无碳中间包干式料的研究与应用

采用新型无碳结合剂取代酚醛树脂研制出一种新型环保无碳干式料,并研究了无碳结合剂加入量对干式料性能的影响。结果表明:偏硅酸盐加入量为8%时,干式料综合性能较为优异。引入橄榄砂能够有效降低干式料热膨胀性能及烧结性能,但是抗渣性能较镁质材料略差。研制的环保无碳干式料可以满足钢厂浇注超低碳钢的使用要求,不会使钢水增碳,环境友好,弥补了树脂结合干式料在低碳、环保方面的不足。

碳基无金属纳米材料用于电催化合成小分子化学品

电催化是各种以化学品形式储存可再生电力能源技术的核心。目前,贵金属基催化剂广泛应用于提高电催化转化效率。然而,成本高、稳定性差等缺点严重阻碍了其在电合成和可持续能源器件中的大规模应用。碳基无金属催化剂(CMFCs)在提高催化性能方面展现出巨大潜力,且受到越来越多的关注。本文概述了用于电催化合成的CMFCs的最新研究进展,并讨论了其催化机理和设计策略。此外,简要总结了电催化合成过氧化氢、氨、氯以及各种碳基和氮基化合物的研究现状,并重点阐述了CMFCs目前面临的挑战和未来前景。