Optimizing band structure of CoP nanoparticles via rich-defect carbon shell toward bifunctional electrocatalysts for overall water splitting

Transition-metal phosphides(TMPs)with high catalytic activity are widely used in the design of electrodes for water splitting.However,a major challenge is how to achieve the trade-off between activity and stability of TMPs.Herein,a novel method for synthesizing CoP nanoparticles encapsu-lated in a rich-defect carbon shell(CoP/DCS)is developed through the self-assembly of modified polycyclic aromatic molecules.The graft and removal of high-activity C-N bonds of aromatic molecules render the controllable design of crystallite defects of carbon shell.The density functional theory calculation indicates that the carbon defects with unpaired electrons could effectively tailor the band structure of CoP.Benefiting from the improved activity and corrosion resistance,the CoP/DCS delivers outstanding difunctional hydrogen evolution reaction(88 mV)and oxygen evolution reaction(251 mV)performances at 10 mA cm^(−2)current density.Furthermore,the coupled water electrolyzer with CoP/DCS as both the cathode and anode presents ultralow cell voltages of 1.49 V to achieve 10 mA cm^(−2)with long-time stability.This strategy to improve TMPs electrocatalyst with rich-DCS and heterogeneous structure will inspire the design of other transition metal compound electrocatalysts for water splitting.

High nitrogen carbon material with rich defects as a highly efficient metal-free catalyst for excellent catalytic performance of acetylene hydrochlorination

In this work,we developed a simple strategy to synthesize a carbon material with high nitrogen and rich carbon defects.Our approach polymerized diaminopyridine(DAP) and ammonium persulfate(APS).Following a range of different temperature pyrolysis approaches,the resulting rough surface was shown to exhibit edge defects due to N-doping on graphite carbon.A series of catalysts were evaluated using a variety of characterization techniques and tested for catalytic performance.The catalytic performance of the N-doped carbon material enhanced alongside an increment in carbon defects.The NC-800 catalyst exhibited outstanding catalytic activity and stability in acetylene hydrochlorination(C_(2) H_(2) GHSV=30 h^(-1),at 220℃,the acetylene conversion rate was 98%),with its stability reaching up to 450 h.Due to NC-800 having a nitrogen content of up to 13.46%,it had the largest specific surface area and a high defect amount,as well as strong C_(2) H_(2) and HCl adsorption.NC-800 has excellent catalytic activity and stability to reflect its unlimited potential as a carbon material.

A new trick on an old support: Zr in situ defects-created carbon nitride for efficient electrochemical nitrogen fixation

Electrochemical nitrogen reduction reaction(NRR) to produce ammonia under ambient conditions is considered as a promising approach to tackle the energy-intensive Haber-Bosch process,but the low Faradaic efficiency and yield of NH_3 are still a challenge.Herein,a carbon-vacancies enriched mesoporous g-C_3 N_4 is developed by an in situ Zr doping strategy.The in situ mesoporous-forming mechanism is deeply understood by TPSR to reveal the functions of Zr dopant that pulls C from the precursor of C_3 N_4,resulting the formation of homogeneous mesopores with about 57% of the one C-defective s-triazine ring in C_3 N_4.Due to the defect sites obtained in metal doping synthesis,the RuAu bimetallic supported catalyst(RuAu_3/0.3 Zr-C_3 N_4) exhibits effective NRR performance with a Faraday efficiency of 11.54% and an NH_3 yield of 5.28 μg h^(-1) mg_(cat) ^(-1).at-0.1 V(RHE),which is nearly 10 times higher than that of RuAu_3/C_3 N_4 catalyst.This work proposes a simple and template-free preparation method for the high defect density mesoporous C_3 N_4,and provides new possibilities of a wide application of mesopore g-C3 N4.

Role of surface defects of carbon nanotubes on catalytic performance of barium promoted ruthenium catalyst for ammonia synthesis

Carbon nanotubes(CNTs) with abundant surface defects are prepared by a liquid oxidation and thermal annealing method. The defective CNTs-D supported Ba–Ru/CNTs-D catalysts exhibit superior catalytic performance in ammonia synthesis with a TOF be increased up to 0.30 s-1, which is 2.5 times of oxidized CNTs-O supported Ba–Ru/CNTs-O catalysts and 5 times of the Ba–Ru/CNTs. The characterizations by CO chemisorption, transmission electron microscope, Raman, and X-ray photoelectron spectroscopy revealed that the uniformly well dispersed Ru NPs can be stabilized on the defective sites of CNTs-D. The great improvement of the catalytic performance and stability of the Ba–Ru/CNTs-D is contributed to the strong interaction between Ru NPs and surface defect of the CNTs.

Creation of surface defects on carbon nanofibers by steam treatment

A direct strategy for the creation of defects on carbon nanofibers (CNFs) has been developed by steam treatment.Nitrogen physisorption,XRD,Raman spectra,SEM and TEM analyses proved the existence of the new defects on CNFs.BET surface area of CNFs after steam treatment was enhanced from 20 to 378 m2/g.Pd catalysts supported on CNFs were also prepared by colloidal deposition method.The different activity of Pd/CNFs catalysts in the partial hydrogenation of phenylacetylene further demonstrated the diverse surfaces of CNFs could be formed by steam treatment.

Effects of doping, Stone Wales and vacancy defects on thermal conductivity of single-wall carbon nanotubes

The thermal conductivity of carbon nanotubes with certain defects （doping, Stone-Wales, and vacancy） is investigated by using the non-equilibrium molecular dynamics method. The defective carbon nanotubes （CNTs） are compared with perfect tubes. The influences of type and concentration of the defect, length, diameter, and chirality of the tube, and the ambient temperature are taken into consideration. It is demonstrated that defects result in a dramatic reduction of thermal conductivity. Doping and Stone-Wales （SW） defects have greater effect on armchair tubes, while vacancy affects the zigzag ones more. Thermal conductivity of the nanotubes increases, reaches a peak, and then decreases with increasing temperature. The temperature at which the thermal conductivity peak occurs is dependent on the defect type. Different from SW or vacancy tubes, doped tubes are similar to the perfect ones with a sharp peak at the same temperature. Thermal conductivity goes up when the tube length grows or diameter declines. It seems that the length of thermal conductivity convergence for SW tubes is much shorter than perfect or vacancy ones. The SW or vacancy tubes are less sensitive to the diameter change, compared with perfect ones.

Thermal conductivity of carbon nanotube superlattices:Comparative study with defective carbon nanotubes

We use molecular dynamics simulation to calculate the thermal conductivities of（5, 5） carbon nanotube superlattices（CNTSLs） and defective carbon nanotubes（DCNTs）, where CNTSLs and DCNTs have the same size. It is found that the thermal conductivity of DCNT is lower than that of CNTSL at the same concentration of Stone–Wales（SW） defects. We perform the analysis of heat current autocorrelation functions and observe the phonon coherent resonance in CNTSLs, but do not observe the same effect in DCNTs. The phonon vibrational eigen-mode analysis reveals that all modes of phonons are strongly localized by SW defects. The degree of localization of CNTSLs is lower than that of DCNTs, because the phonon coherent resonance results in the phonon tunneling effect in the longitudinal phonon mode. The results are helpful in understanding and tuning the thermal conductivity of carbon nanotubes by defect engineering.

Sustainable Lignin-Derived Carbon as Capacity-Kinetics Matched Cathode and Anode towards 4.5 V High-Performance Lithium-Ion Capacitors

The Li-ion capacitors(LICs)develop rapidly due to their double-high features of high-energy density and high-power density.However,the relative low capacity of cathode and sluggish kinetics of anode seriously impede the development of LICs.Herein,the precisely pore-engineered and heteroatomtailored defective hierarchical porous carbons(DHPCs)as large-capacity cathode and high-rate anode to construct high-performance dual-carbon LICs have been developed.The DHPCs are prepared based on triple-activation mechanisms by direct pyrolysis of sustainable lignin with urea to generate the interconnected hierarchical porous structure and plentiful heteroatominduced defects.Benefiting from these advanced merits,DHPCs show the well-matched high capacity and fast kinetics of both cathode and anode,exhibiting large capacities,superior rate capability and long-term lifespan.Both experimental and computational results demonstrate the strong synergistic effect of pore and dopants for Li storage.Consequently,the assembled dual-carbon LIC exhibits high voltage of 4.5 V,high-energy density of 208 Wh kg^(−1),ultrahigh power density of 53.4 kW kg^(−1)and almost zerodecrement cycling lifetime.Impressively,the full device with high mass loading of 9.4 mg cm^(−2)on cathode still outputs high-energy density of 187 Wh kg^(−1),demonstrative of their potential as electrode materials for high-performance electrochemical devices.

Mono-Vacancy and B-Doped Defects in Carbon Heterojunction Nanodevices

We present a detailed theoretical study of the behavior of mono-vacancy and B-doped defects in carbon heterojunction nanodevices. We have introduced a complete set of formation energy and surface reactivity calculations, considering a range of different diameters and chiralities of combined carbon nanotubes. We have investigated three distinct combinations of carbon heterojunctions using density functional theory (DFT) and applying B3LYP/3-21g: armchair-armchair herteojunctions, zigzag-zigzag heterojunctions, and zigzag-armchair heterojunctions. We have shown for first time a detailed study of formation energy of mono-vacancy and B-doped defects of carbon heterojunction nanodevices. Our calculations show that the highest surface reactivity is found for the B-doped zigzag-armchair heterojunctions and it is easier to remove the carbon atom from the network of heterojunction armchair-armchair CNTs than the heterojunction zigzag-armchair and zigzag-zigzag CNTs.

Stability and Electronic Properties of Hydrogenated Zigzag Carbon Nanotube Focused on Stone-Wales Defect

We present a first-principles study of the chemisorption of hydrogen on a Stone-Wales （SW） defective carbon nanotube （10,0）. The investigated configurations include four configurations covering single defects and double defects. One hydrogen dimer adsorption is energetically favored on bonds shared by carbon heptagon-heptagon for configurations with the defect parallel to the tube axis compared with the carbon pentagon-hexagon sites for ones with a slanted defect. This different behavior is also demonstrated for hydrogen dimer chain adsorption, the favored site for the former ones is through the defect, which is the nearest neighbor site to defect for the latter ones. It is found that the energy band gaps of hydrogenated configurations may be enlarged or decreased by altering the adsorption site or defect position. The semiconductor-to-metal transition may occur for configurations with the defect or defects parallel to the tube axis due to low electronic localization. Our results highlight the interest of the interaction of multi-factor system by providing a detailed bond and position picture of a hydrogenated defective carbon nanotube （10,0）.

Thermally Agitated Self Assembled Carbon Nanotubes and the Scenario of Extrinsic Defects

Employing the arc discharge method we prepared carbon nanotubes, CNTs, in open air deionized water. Their morphology was studied varying the annealing temperature and characterizing by Raman Spectroscopy, Transmission Electron Microscopy (TEM), X-Ray Diffractogram (XRD) and Energy Dispersion X-Ray (EDX). According to the study, the CNTs are found self-assembled where the graphene sheets and/or defects are observed sort out themselves with enhancement of temperature.

Effect of Monovacancy Defects on Adsorbing of CO, CO₂, NO and NO₂on Carbon Nanotubes: First Principle Calculations

We have applied density functional theory to investigate different types of carbon nanotubes (armchair (4,4)CNT and zig-zag (7,0)CNT) as sensors of some pollutant gas molecules, especially CO, CO2, NO and NO2. We show, for the first time, that the adsorption of pollutant gas molecules on carbon nanotubes are improved by introducing the monovacancy defects on the surfaces of (7,0)CNT. The adsorption energies, the optimal adsorption positions and the orientation of these gas molecules on the surfaces of carbon nanotubes are studied. It is found that the most adsorbed pollutant gas is NO molecule on (7,0)CNT.

Radial collapse and physical mechanism of carbon nanotube with divacancy and 5-8-5 defects

By employing molecular mechanics and molecular dynamics simulations, we investigate the radial collapses and elasticities of different chiral single-walled carbon nanotubes （SWCNTs） with divacancy, and 5-8-5 defects. It is found that divacancy and 5-8-5 defect can reduce the collapse pressure （Pc） of SWCNT （10, 10） while 5-8-5 defect can greatly increase Pc of SWCNT （17, 0）. For example, 5-8-5 defect can make Pc of SWCNT （17, 0） increase by 500%. A model is established to understand the effects of chirality, divacancy, and 5-8-5 defect on radial collapse of SWCNTs. The results are particularly of value for understanding the mechanical behavior of SWCNT with divacancy, and the 5-8-5 defect that may be considered as a filler of high loading composites.

Prevention of burn-on defect on surface of hydroturbine blade casting of ultra-low-carbon refining stainless steel

The burn-on sand is common surface defect encountered in CO2 -cured silicate-bonded sand casting of hydroturbine blade of ultra-low-carbon martensitic stainless steel,its feature,causes and prevention measures are presented in this paper.Experiments showed that the burn-on defect is caused by oxidization of chromium in the molten steel at high temperature and can be effectively eliminated by using chromium-corundum coating.

Investigation of Mechanical Behavior of Defective Carbon Nanotubes Using Molecular Dynamics Simulation

Carbon nanotubes （CNTs） having pristine structure （i.e., structure without any defect） hold very high mechanical properties. However, CNTs suffer from defects ＇which can appear at production stage, purification stage or be deliberately introduced by irradiation with energetic particles or by chemical treatment. In this article, mechanical properties of single-walled nanotubes with defects are studied under both compressive and tensile loads using molecular dynamics （MD） simulations. Two types of defectStone-Wales and vacancy defects with different defect densities are considered for present investigation. Molecular simulations are carried out using the classical MD method. The Brenner potential is used for carbon-carbon interaction in the CNT. Temperature of the system is controlled by velocity scaling. Simulation results show that the defects have negligible effect on the modulus of elasticity of nanotubes. However, they have significant effect on the failure stress and strain of the nanotubes.

含缺陷管道碳纤维复合材料补强数值模拟研究

当代石油、天然气等能源的主要运输方式为管道运输,管道在长期使用时会产生各种缺陷,这些缺陷将对管道的结构和强度产生影响。目前先进的管道修复技术为复合材料补强技术,其中碳纤维复合材料是较优的选择。为了测试有/无碳纤维补强管道缺陷处的效果,开展了不同层数碳纤维复合材料的拉伸实验研究,结合ANSYS数值模拟探究了修复前后不同缺陷管道在承载时的应力、应变分布,分析了修复补强效果的影响因素。结果表明:缺陷减薄厚度对管道的应力、应变状态影响较大,碳纤维复合材料修复技术能在减小管道缺陷处应力、应变的同时优化其应力、应变分布,可以通过增加碳纤维修复层数来提升修复效果,相关研究对于管道的修复补强有一定指导意义。

γ射线辐照硬碳结构演化及其储钠性能

通过γ射线辐照技术引入“自掺杂”缺陷,优化硬碳层间尺寸和孔结构。通过扫描电镜、X射线衍射、拉曼光谱、等温氮气吸脱附等方法探究了吸收剂量对硬碳层间距与内部缺陷、无序结构的影响;通过恒电流充/放电研究了材料的电化学性能。结果表明:较低剂量辐照会提升硬碳表面结晶度,而随着吸收剂量的增加,硬碳无序结构增多,辐照后硬碳电化学性能得到明显改善。在140 kGy剂量辐照下,硬碳呈现出425.343 m^(2)/g的高比表面积,硬碳在30 mA/g能够提供300 mAh/g的储钠容量,在1 A/g大电流密度容量仍然保持在195 mAh/g,对比未辐照处理的硬碳,电极容量提高了3倍,并且在大倍率充/放电过程中保持优良的稳定性能。这项工作为设计先进的纳米材料及缺陷工程在储能领域的应用提供了新的途径和思路。

炭黑负载增加活性炭缺陷位点催化甲烷裂解制氢机理研究

在“双碳”目标时代背景下,甲烷催化裂解制氢因无CO_(2)排放被认为是一种很有前途的高纯制氢技术。其中针对碳基催化剂改性的研究是一大关注热点。为提高活性炭(Activated Carbon,AC)催化剂的稳定性,提出了以椰壳活性炭负载科琴黑炭黑(Carbon Black,CB)制备的新型催化剂,并对其进行了表征测试分析、催化甲烷裂解实验以及分子模拟计算。实验结果表明:分散剂使用1 g、AC和CB质量配比8∶2时制备的催化剂具有较好的催化性能,反应温度在1000℃时初始活性高达85%以上,延缓失活15 min,反应中期甲烷转化率比AC最高提升8%左右。这是因为CB负载在AC表面经反应生成具有缺陷位点的沉积碳。分子模拟计算结果显示,主要是拓扑缺陷的存在使得其s、p轨道非局域性增大,提高其甲烷吸附性能,促进反应进行。同时,AC表面的微孔以及羧基、羰基、羟基等含氧官能团也对甲烷分子的吸附有不同程度的促进作用。孔径为0.8 nm时吸附热最大,这意味着微孔的存在有利于甲烷在AC上吸附,特别是小微孔;3种官能团均可以促进甲烷在AC表面的吸附,其中羧基促进作用更好,羰基和羟基效果相差不大。

碳基电催化剂缺陷工程用于CO_(2)还原反应

电催化二氧化碳(CO_(2))还原是通过电能将温室气体CO_(2)转化为高附加值化学品。碳基材料因其成本低、活性高的特点,被广泛应用于包括电催化CO_(2)还原在内的多种电化学反应中。近年来,通过缺陷工程在碳基材料中构建不对称中心优化材料的物理化学性质,提高电催化活性这一策略引起了研究人员的广泛关注。本文综述了缺陷碳基材料的类型、构建方法和缺陷表征方法,并进一步梳理了缺陷工程的优势、各种缺陷构建方法和表征方法的优缺点。最后,对缺陷碳基材料在电催化CO_(2)还原中面临的挑战和机遇进行了展望。相信本文能为缺陷碳基材料在CO_(2)还原中的发展提供针对性的建议。

磷掺杂氮缺陷g-C_(3)N_(4)的合成及其光催化性能研究

以二氰胺和硫脲为混合前驱体,(NH4)2HPO4为磷源,采用热聚合联合快速高温法合成了磷掺杂氮缺陷石墨相氮化碳(g-C_(3)N_(4)),考察了前驱体配比、磷掺杂量和高温处理温度对g-C_(3)N_(4)结构和光催化活性的影响。结果表明,硫脲与二氰胺质量比为6∶4,磷掺杂量为5%,高温处理温度为700℃时,得到样品(DS60-5%-700)光催化性能最优。其在60min时对亚甲基蓝的降解效率为96.15%,分别较DS60-5%和DS60%提升了1.24倍和1.5倍。P掺杂和快速高温处理降低了g-C_(3)N_(4)的带隙值,扩宽了可见光的吸收范围,同时在g-C_(3)N_(4)结构中进入了氮缺陷,促使光生载流子的有效分离。