Prussian blue analogue derived NiCoSe4 coupling with nitrogen-doped carbon nanofibers for pseudocapacitive electrodes

The design of pseudocapacitive materials by coupling transition metal compounds with a conductive carbon matrix is important for the high performance of supercapacitors. Herein, we construct the Prussian blue analogue derived nickel-cobalt selenides coupling with nitrogen-doped carbon nanofibers (NiCoSe₄-NCNFs) by carbonization and selenization of polyacrylonitrile nanofibers. The effect of selenization and element N doping on the morphological structure and surface chemistry of NiCoSe₄-NCNFs are evaluated. Due to the accelerated electrolyte ion diffusion, enlarged active surface area and the modified surface chemistry by the strong interaction at NiCoSe₄/NCNFs interfaces, NiCoSe₄-NCNFs show excellent capacitive behaviors in 1 mol/L KOH, and the specific capacitance is 1257 F/g at 1 A/g with a rate capability of 78% and cyclic stability of 82.9%. The Gibbs free energy of adsorption OH⁻ is calculated by density functional theory to investigate the charge storage mechanism. This work offers a new strategy to construct the transition metal selenides/carbon nanofibers hybrids for high-performance supercapacitor devices.     

Pt/CNTs催化剂的制备及其催化臭氧化活性研究

以碳纳米管(CNTs)为催化剂载体, 以H₂PtCl₆•6H₂O为贵金属活性组分前驱物, 采用等体积浸渍法制备了Pt/CNTs催化剂. 以草酸为目标污染物, 考察了所制备催化剂的催化活性, 并采用SEM, XRD和XPS等分析方法对催化剂进行表征. 对活性组分Pt的负载量、氢还原温度和热处理方式进行了研究, 确定了适宜的制备条件为Pt负载量1.0%、氢还原温度350 ℃. 研究表明, 在本实验条件下, 单独臭氧氧化、碳纳米管载体催化臭氧化和Pt/CNTs催化臭氧化分别能去除溶液中3.0%, 72.9%和97.9%的草酸. Pt的负载明显地提高碳纳米管催化臭氧化的效果. XRD分析显示催化剂的活性组分Pt以单质Pt⁰的形式存在; 与氢还原过程相比, 在空气气氛中焙烧制备的Pt/CNTs催化剂表面Pt的结晶度过高, 而且XPS结果表明此催化剂表面的Pt有化学吸附氧存在, 导致催化活性降低.     

Electrodeposition of Platinum Nanoparticles on Multi-Walled Carbon Nanotubes for Electrocatalytic Oxidation of Methanol

Platinum (Pt) nanoparticles were deposited at the surface of well-aligned multi-walled carbon nanotubes (MWNTs) by potential cycling between +0.50 and −0.70 V at a scanning rate of 50 mV · s⁻¹ in 5 mM Na₂PtCl₆ solution containing 0.1 M NaCl. The electrocatalytic oxidation of methanol at the nanocomposites of Pt nanoparticles/nanotubes (Pt_nano/MWNTs) has been investigated using 0.2 M H₂SO₄ as supporting electrolyte. The effects of various parameters, such as Pt loading, concentration of methanol, medium temperature as well as the stability of Pt_nano/MWNTs electrode, have been studied. Compared to glassy carbon electrode, carbon nanotube electrode significantly enhances the catalytic efficiency of Pt nanoparticles for methanol oxidation. This improvement in performance is due not only to the high surface area and the fast electron transfer rate of nanotubes but also to the highly dispersed Pt nanoparticles as electrocatalysts at the tips and the sidewalls of nanotubes.     

PtRu/氮掺杂碳电催化甲醇氧化及电解水析氢性能

将三聚氰胺、RuCl₃及炭黑以一定的比例分散于乙醇中,采用旋转蒸干及高温热处理合成了一种氮掺杂碳(NC)负载Ru的Ru/NC催化剂。采用硼氢化钠液相化学还原法合成了不同Pt、Ru负载量的PtRu/NC催化剂,并用于电催化甲醇氧化反应(MOR)及电催化分解水析氢反应(HER)。结果表明,合成的催化剂中Pt₁Ru/NC(Pt、Ru的实际负载量分别为1.14%、0.54%)表现出最优的MOR性能,质量活性达4.96 A·mg^-1_PtRu,且经10 000 s稳定性测试后质量活性保持在测试前的91.1%。同时,当电流密度为100mA·cm^-2时,Pt₁Ru/NC在 HER中表现出最低的过电位(103 mV)和最小的 Tafel斜率(15.29 mV·dec^-1)。通过 X射线衍射(XRD)、X射线光电子能谱(XPS)、透射电子显微镜(TEM)、扫描透射电子显微镜(STEM)、电感耦合等离子体发射光谱(ICP-OES)、STEM-能谱(STEM-EDS)技术表征了PtRu/NC双金属催化剂,其具有优异催化性能的原因如下：(1) PtRu双金属纳米颗粒高度分散于NC上;(2) Pt以纳米团簇或单原子形式负载于Ru上,后负载于NC,形成了Pt-Ru相分离结构;(3) Pt、Ru与N之间存在协同效应。     

Revealing the Effect of Surface Composition on Multiwalled Carbon Nanotubes Supported Pt-Fe Alloy Electrocatalysts for Methanol Oxidation Performance

The designs of efficient and inexpensive Pt-based catalysts for methanol oxidation reaction (MOR) are essential to boost the commercialization of direct methanol fuel cells. Here, the highly catalytic performance PtFe alloys supported on multiwalled carbon nanotubes (MWCNTs) decorating nitrogen-doped carbon (NC) have been successfully prepared via co-engineering of the surface composition and electronic structure. The Pt₁Fe₃@NC/MWCNTs catalyst with moderate Fe³⁺ feeding content (0.86 mA/mg_Pt) exhibits 2.26-fold enhancement in MOR mass activity compared to pristine Pt/C catalyst (0.38 mA/mg_Pt). Furthermore, the CO oxidation initial potential of Pt₁Fe₃@NC/MWCNTs catalyst is lower relative to Pt/C catalyst (0.71 V and 0.80 V). Benefited from the optimal surface compositions, the anti-corrosion ability of MWCNT, strong electron interaction between PtFe alloys and MWCNTs and the N-doped carbon (NC) layer, the Pt₁Fe₃@NC/MWCNTs catalyst presents an improved MOR performance and anti-CO poisoning ability. This study would open up new perspective for designing efficient electrocatalysts for the DMFCs field.     

Carbon Nanotube@N‐Doped Mesoporous Carbon Composite Material for Supercapacitor Electrodes

Here, carbon nanotube@N‐doped mesoporous carbon (CNT@N‐PC) composites were synthesized by using resorcinol‐formaldehyde resin as carbon source, ionic liquids (ILs) as template, and nitrogen sources and tetraethyl orthosilicate (TEOS) as assistant agent. The use of ILs‐modified CNT with nitrogen and TEOS facilitated the generation of a richer mesoporous structure. The obtained CNT@N‐PC was composed of a CNT core and mesoporous carbon particles around it. CNT@N‐PC showed a 3D network structure like “dewy cobwebs” and had a high surface area of 857 m² g^?1, uniform pore size distribution (3.0 nm), and suitable N content (4.9 at.%). When used as supercapacitor electrode, the CNT@N‐PC exhibited a high specific capacitance (244 F g^?1 at 1 A g^?1), good rate capability and favorable capacitance retention (92.5 % capacitive retention after 5000 cycles), demonstrating the potential for application in high‐performance supercapacitors.     

Hierarchical Activated Mesoporous Phenolic‐Resin‐Based Carbons for Supercapacitors

A series of hierarchical activated mesoporous carbons (AMCs) were prepared by the activation of highly ordered, body‐centered cubic mesoporous phenolic‐resin‐based carbon with KOH. The effect of the KOH/carbon‐weight ratio on the textural properties and capacitive performance of the AMCs was investigated in detail. An AMC prepared with a KOH/carbon‐weight ratio of 6:1 possessed the largest specific surface area (1118 m² g^?1), with retention of the ordered mesoporous structure, and exhibited the highest specific capacitance of 260 F g^?1 at a current density of 0.1 A g^?1 in 1 M H₂SO₄ aqueous electrolyte. This material also showed excellent rate capability (163 F g^?1 retained at 20 A g^?1) and good long‐term electrochemical stability. This superior capacitive performance could be attributed to a large specific surface area and an optimized micro‐mesopore structure, which not only increased the effective specific surface area for charge storage but also provided a favorable pathway for efficient ion transport.     

Phenylenediamine-formaldehyde chemistry derived N-doped hollow carbon spheres for high-energy-density supercapacitors

Porous carbon spheres represent an ideal family of electrode materials forsupercapacitors because of the high surface area,ideal conductivity,negligible aggregation,and ability to achieve space efficient packing.However,the development of new synthetic methods towards porous carbon spheres still remains a great challenge.Herein,N-doped hollow carbon spheres with an ultrahigh surface area of2044 m²/g have been designed based on the phenylenediamine-formaldehyde chemistry.When applied in symmetric supercapacitors with ionic electrolyte(EMIBF_4),the obtained N-doped hollow carbon spheres demonstrate a high capacitance of 234 F/g,affording an ultrahigh energy density of 114.8 Wh/kg.Excellent cycling stability has also been achieved.The impressive capacitive performances make the phenylenediamine-formaldehyde resin derived N-doped carbon a promising candidate electrode material for supercapacitors.     

Synthesis of Sub‐nanometer Porous Carbon Film for Energy Storage

Carbon‐based supercapacitors are a kind of supercapacitors with very promising applications because of their low cost, good stability and adjustable properties. Simple and rapid syntheses of carbon materials with a high surface area and narrow pore size distribution are of great significance to practical applications of carbon‐based supercapacitors. Here we report a new strategy to synthesize sub‐nanometer porous carbon films (Snp‐CF) via a condensation reaction under mild conditions. Carbon films exhibit a narrow pore size distribution (6.6 Å) and high surface area (508 m² g^?1) after annealing at 700 °C. Snp‐CF‐700 displays a good specific capacity and excellent cycle performance (130 F g^?1 after 5000 cycles, 118 % of initial 110 F g^?1).     

Facile and Large-Scale Fabrication of Sub-3 nm PtNi Nanoparticles Supported on Porous Carbon Sheet: A Bifunctional Material for the Hydrogen Evolution Reaction and Hydrogenation

Facile and large-scale preparation of materials with uniform distributions of ultrafine particles for catalysis is a challenging task, and it is even more difficult to obtain catalysts that excel in both the hydrogen evolution reaction (HER) and hydrogenation, which are the corresponding merging and splitting procedures of hydrogen, respectively. Herein, the fabrication of ultrafine bimetallic PtNi nanoparticles embedded in carbon nanosheets (CNS) by means of in situ self-polymerization and annealing is reported. This bifunctional catalyst shows excellent performance in the hydrogen evolution reaction (HER) and the hydrogenation of p-nitrophenol. Remarkably PtNi bimetallic catalyst with low metal loading (PtNi₂@CNS-600, 0.074 wt % Pt) exhibited outstanding HER activity with an overpotential as low as 68 mV at a current density of 10 mA cm⁻² with a platinum loading of only 0.612 μg_Pt cm⁻² and Tafel slope of 35.27 mV dec⁻¹ in a 0.5 m aqueous solution of H₂SO₄, which is comparable to that of the 20 % Pt/C catalyst (31 mV dec⁻¹). Moreover, it also shows superior long-term electrochemical durability for at least 30 h with negligible degradation compared with 20 % Pt/C. In addition, the material with increased loading (mPtNi₂@CNS-600, 2.88 % Pt) showed robust catalytic activity for hydrogenation of p-nitrophenol at ambient pressure and temperature. The catalytic activity towards hydrogen splitting is a circumstantial evidence that agrees with the Volmer–Tafel reaction path in the HER.     

高功率超级电容器用介孔炭电极材料

以纳米CaCO3为模板、蔗糖为前躯体制备超级电容器用介孔炭电极材料.材料的结构由氮吸附、TEM表征,借助恒流充放电、循环伏安和交流阻抗评价了其在6 mol.L-1KOH电解液中的电化学电容性能.结果表明,蔗糖基介孔炭的比表面积606 m2/g,富含10~30 nm的介孔.恒流放电法测得介孔炭在电流密度50 mA/g下的比电容为125 F/g,大电流倍率性能特别突出.电流密度增大到20 000 mA/g,比电容还保持有88F/g,远高于进口电容炭,该介孔炭是一种很有前景的高功率超级电容器炭电极材料.     

Mesoporous Carbons Templated by PEO-PCL Block Copolymers as Electrode Materials for Supercapacitors

In this study, samples of activated mesoporous carbon are fabricated with pore structures with cylinder and gyroid nanostructures through the templating effect of amphiphilic poly(ethylene oxide-block-caprolactone) (PEO-PCL) and by using specific resol/PEO-PCL weight ratios (e.g., 60:40 for cylinders; 55:45 for gyroids). After carbonization and KOH activation, the activated mesoporous carbons were tested as electrode materials for electric double-layer capacitor (EDLC) supercapacitors. The electrochemical properties were examined by using three-electrode (6 m KOH_(aq) as electrolyte) and CR2032 coin-cell (1 m tetraethylammonium tetrafluoroborate (TEABF₄)/CN as the electrolyte) systems. The gyroid carbon samples provided specific capacitances higher than those of the cylinder carbon samples in both aqueous and organic systems: 155 F g⁻¹ compared with 135 F g⁻¹ in 6 m KOH_(aq), and 105.6 compared with 96 F g⁻¹ in 1 m TEABF₄/MeCN, after 100 charge/discharge cycles. It is suspected that the bi-continuous mesochannels of the gyroid-type activated mesoporous carbons provided a relatively higher effective adsorption surface area; in other words, the greater surface area for energy storage originated from a moderate pore size and an interconnected pore structure.     

Stabilizing a Platinum1 Single‐Atom Catalyst on Supported Phosphomolybdic Acid without Compromising Hydrogenation Activity

In coordination chemistry, catalytically active metal complexes in a zero‐ or low‐valent state often adopt four‐coordinate square‐planar or tetrahedral geometry. By applying this principle, we have developed a stable Pt₁ single‐atom catalyst with a high Pt loading (close to 1 wt %) on phosphomolybdic acid(PMA)‐modified active carbon. This was achieved by anchoring Pt on the four‐fold hollow sites on PMA. Each Pt atom is stabilized by four oxygen atoms in a distorted square‐planar geometry, with Pt slightly protruding from the oxygen planar surface. Pt is positively charged, absorbs hydrogen easily, and exhibits excellent performance in the hydrogenation of nitrobenzene and cyclohexanone. It is likely that the system described here can be extended to a number of stable SACs with superior catalytic activities.     

KOH Direct Activation for Preparing Activated Carbon Fiber from Polyacrylonitrile-based Pre-oxidized Fiber

The activated carbon fiber（ACF） was prepared from polyacrylonitrile-based pre-oxidized fiber（PANOF） by KOH direct activation. The influence of activation conditions including impregnation ratio（the mass ratio of PANOF to KOH）, activation temperature and activation time on the pore structure and electrochemical properties of ACF was investigated, and the corresponding activation mechanism was proposed. The ACF prepared at an activation temperature of 800℃ and an impregnation ratio（the mass ratio of PANOF to KOH） of 1：2 for an activation time of 1 b in 6 mol/L KOH solution exhibits a specific surface area of 3029 m^2/g, a mesoporosity of 84.2% and a specific capacitance of 288 F/g, and shows a good capacitive performance. The prepared ACF can be used as the electrode material for supercapacitors.     

Catalytic and physicochemical properties of Pt/α-GeO<Subscript>2</Subscript> systems in reaction of selective hydrogenation of α,β-unsaturated aldehydes in a gas phase

Hydrogenation of crotonaldehyde in a gas phase over Pt/α-GeO₂ catalysts was investigated. The systems were characterized by BET, XRD, TPR, TEM, ToF-SIMS, and FTIR methods. The optimum pretreatment parameters were studied. The best catalytic performance shows the catalyst 5 wt % Pt/α-GeO₂ (69% selectivity to crotyl alcohol at 200 μmol s⁻¹ g _Pt ⁻¹ activity and 10% conversion of crotonaldehyde). Lower loaded catalysts (2 and 1 wt % Pt) show lower, but also promising activity and selectivity. This good catalytic performance was related to the physicochemical properties of the catalyst. GeO₂ in the presence of Pt undergoes a partial surface reduction at temperatures higher than 100°C probably leading to the creation of the active Pt-Ge centers responsible for high selectivity to crotyl alcohol. Reduction at a temperature≥200°C deactivates the catalytic systems due to the formation of inactive PtGe alloys. Published in Russian in Kinetika i Kataliz, 2007, Vol. 48, No. 4, pp. 600–605. This article was submitted by the authors in English.     

Promising activated carbons derived from cabbage leaves and their application in high-performance supercapacitors electrodes

In this paper, cabbage leaves (CLs) were used to synthesize porous activated carbon by the carbonization and activation processes. The material for CLs were carbonized at 600 °C and activated at 800 °C with the KOH/C-600 mass ratio 4 (denoted as AC-800) show typical amorphous character and display porous structures with high specific surface areas 3102 m²/g via XRD and BET measurements. As the electro-active material, AC-800 electrode exhibit ideal capacitive behaviors in aqueous electrolytes and the maximal specific capacitance is as high as 336 F/g at the current density of 1 A/g. Furthermore, AC-800 electrode shows excellent electrochemical cycle stability with ～95 % initial capacitance being retained after 2000 cycles. The desirable capacitive performances enable the CLs to act as a new biomass source of carbonaceous materials for high-performance supercapacitors and low-cost electrical energy storage devices.     

Preparation of activated carbon from Turbinaria turbinata seaweeds and its use as supercapacitor electrode materials

Turbinaria turbinata brown seaweeds were tested as carbon electrode material in symmetric, electrochemical supercapacitors. The electrochemical properties of the carbon materials were characterised for their application as supercapacitors using cyclic voltammetry, galvanostatic charge/discharge method and electrochemical impedance spectroscopic analyses. Our initial results showed that the optimal behaviour was obtained for the sample prepared by pyrolysis at 800 °C. The average surface area of the carbon was 812 m²/g. Electrochemical tests with an organic electrolyte gave the following interesting results: a capacitance of 74.5 F/g, a specific series resistance of 0.5 Ω cm² and an ionic resistivity of 1.3 Ω cm². These results show the promising capacitive properties of carbon derived from seaweeds and their application in electrochemical supercapacitors.     

活性炭孔隙结构对催化氧化脱除单质汞的影响

研究活性炭在硫化氢存在条件下催化氧化脱除煤气中单质汞的吸附机理和探讨提高其吸附能力的方法,在模拟煤气气氛下对3种活性炭和一种活性焦进行汞的吸附性能实验,并进一步分析活性炭(焦)的孔隙结构。用BET方程处理N₂等温吸附数据,计算比表面积;用HK法进行微孔分析;用BJH法计算中孔孔径分布。结果表明,硫化氢被催化氧化后,生成吸附在活性炭孔壁上的活性硫促进了对汞的吸附;随着活性炭微孔和中孔体积的增大,活性炭对汞的吸附能力得到提高。     

Comparative evaluation of xerogel-based activated carbons synthesized from aliphatic aldehydes of different chain lengths

This work deals with examining the performance of xerogel-based activated carbons (XACs), which were synthesized from aliphatic aldehydes of different carbon chain lengths. These XACs were compared with those synthesized from commonly synthesized XACs. The performance of the new xerogels was determined by examining the thermo-gravimetric analysis (TGA) and Fourier transform infrared (FTIR); however, the XACs were studied using infrared spectra (IR), scanning electron microscopy (SEM), and their adsorption capacities in gas and aqueous media (nitrogen adsorption, iodine number, adsorption of phenol and methylene blue, MB). The adsorption behavior of these investigated XACs to MB was studied in detail, using the Langmuir and Freundlich adsorption equations, in addition to kinetic (Lagergren first-order and pseudo-second-order) and thermodynamic models. The results show that long -chain aldehydes have a significant effect on increasing the total pore volume (V_T). Glutaraldehyde-based carbon xerogel is recommended as an economically superior adsorbent with an S_BET x yield of 571.9 m²/g. XACs from glutaraldehyde and propionaldehyde have higher surface area than commonly synthesized ACs from formaldehyde (F), Phenol/F, Tanin/F-, Polybenzooxazine/F, and Pyrogallol/F. The best models used for MB adsorption onto XACs are Langmuir and pseudo-second-order kinetic equations. The negative values of thermodynamic parameter ΔGº and positive values of ΔHº indicate the MB adsorption process is spontaneous and endothermic.     

Mesopore-dominant porous carbon derived from bio-tars as an electrode material for high-performance supercapacitors

For the first time, toxic bio-tars collected from the gasification of pine sawdust are used as the precursor for activated carbons. Various types of activation agents including KOH, K₂CO₃, H₃PO₄ and ZnCl₂ were screened for obtaining superior activated carbons. When KOH was used as an activation agent, the obtained activated carbons exhibited high specific surface area and large mesopore volume. The activated carbons were further employed to be the electrode material of supercapacitors, and its specific capacitance reached up to 260 F g^?1 at 0.25 A g^?1 current density. Also, it showed an excellent rate performance from preserving a relatively high specific capacitance of 151 F g^?1 at 50 A g^?1. The assembled device also exhibited the good electrochemical stability with the capacity retention of 90% after 5000 cycles. Furthermore, the maximum energy density of the activated carbons in organic electrolyte reached 17.8 Wh kg^?1.