Activity of PtSnRh/C nanoparticles for the electrooxidation of C1 and C2 alcohols

A systematic investigation of alcohol adsorption and oxidation on binary and ternary electrocatalysts in acid medium was performed. Binary (PtRh) and ternary (PtRhSn) were prepared by the Pechini modified method on carbon Vulcan XC-72, and different nominal compositions were characterized by energy dispersive X-ray and X-ray diffraction (XRD) techniques. The XRD results showed that the Pt₈₀Rh₂₀/C and Pt₇₀Sn₁₀Rh₂₀/C electrocatalysts consisted of the Pt displaced phase, suggesting the formation of a solid solution between the metals Pt/Rh and Pt/Sn.Electrochemical investigations on these different electrode materials were carried out as a function of the electrocatalyst composition, in acid medium (0.5 mol dm^− 3 H₂SO₄), and in the absence and presence of different alcohols (methanol, ethanol and ethylene glycol). The electrochemical results obtained at room temperature have shown that the Pt₇₀Sn₁₀Rh₂₀/C catalyst display better catalytic activity for alcohol oxidation compared with the binary catalyst.In situ reflectance infrared spectroscopy measurements have shown that the oxidation of alcohols mentioned produced CO₂ at low potentials indicating that the materials synthesized could be used as efficient anodes in the fuel cell applications.     

炭气凝胶负载Pt基催化剂的制备及其甲醇氧化催化性能

以间苯二酚(R)和甲醛(F)为原料,制备R-F炭气凝胶(RF-CAs).继以后者为载体采用浸渍还原法制备铂基催化剂Pt/CA,并比较其与由相同负载工艺制得的以Vulcan XC-72为载体的铂基催化剂Pt/XC72的催化甲醇氧化反应的性能.结果表明,前者具明显高的甲醇氧化催化活性,显示CAs是一种极具潜在竞争力的燃料电池催化剂载体材料.     

Mesoporous carbon spheres with uniformly penetrating channels and their use as a supercapacitor electrode material

An optimized nanostructure design for electrode materials of supercapacitors was realized by introducing furfuryl alcohol into as-prepared surfactant-containing spherical host and generating a robust mesoporous structure. The structural characterization shows that the carbon spheres inherit the regular mesopore structure and high surface area of the template and possess a uniform particle size containing well-ordered channels throughout the spheres. By adjusting the initial molar ratio of H₂O to tetraethyl orthosilicate (TEOS), the pore volumes of the templated carbons vary from 0.4 to 0.6 cm³·g^-1 and surface areas are in the range of 610 and 944 m²·g^-1. Furthermore, NiO nanoparticles were incorporated into the carbon spheres by air oxidation of the Ni-containing samples. The use of these spheres in electrode materials for electric double layer capacitors was investigated. The electrochemical measurements show that the specific capacitance of the ordered mesoporous carbon spheres (OMCs-2) can increase by 40% to 205.3 F·g^-1 by the addition of 3 wt% NiO.     

Regulating the Wettability of Hard Carbon through Open Mesochannels for Enhanced K+ Storage

Hard carbons are deemed as promising anode materials for high-performance potassium-ion battery, but their commercialization is still hindered by the insufficient K⁺ transfer kinetics and poor potassiophilicity. Herein, these issues are addressed by improving the wettability of hard carbon, which can be achieved by the introduction of open mesochannels. A series of such hollow mesoporous carbon capsules with different dimensions are synthesized, which exhibit markedly enhanced wettability with electrolyte compared to the microporous counterparts. Various characterizations confirm its effects on promoting the kinetics and potassiophilicity of as-synthesized carbons, which can be additionally improved by S-doping. As a result, the 2D mesoporous carbon anode exhibits excellent rate capability (122.2 mAh g^-1 at 4 A g^-1), high reversible capacity (396.6 mAh g^-1 at 0.1 A g^-1 after 200 cycles), and outstanding cycling stability (197.0 mAh g^-1 at 2 A g^-1 after 1400 cycles). In addition, the hollow mesoporous architecture can effectively buffer the volume expansion and thus stabilize the carbon anodes, as visualized by in situ transmission electron microscopy. This work provides new insight for enhanced K⁺ storage performance from the perspective of anode wettability with electrolyte, as well as a universal anode design that combines mesochannels architecture with heteroatom doping.     

Ordered Mesoporous Carbons

Ordered mesoporous carbons have recently been synthesized using ordered mesoporous silica templates. The synthesis procedure involves infiltration of the pores of the template with appropriate carbon precursor, its carbonization, and subsequent template removal. The template needs to exhibit three‐dimensional pore structure in order to be suitable for the ordered mesoporous carbon synthesis, otherwise disordered microporous carbon is formed. MCM‐48, SBA‐1, and SBA‐15 silicas were successfully used to synthesize carbons with cubic or hexagonal frameworks, narrow mesopore size distributions, high nitrogen Brunauer–Emmett–Teller (BET) specific surface areas (up to 1800 m² g^–1), and large pore volumes. Ordered mesoporous carbons are promising in many applications, including adsorption of large molecules, chromatography, and manufacturing of electrochemical double‐layer capacitors.     

ZTIFs derived nitrogen-introduced high specific area and hierarchical porous carbon for oxygen reduction reaction

It is of great allure to construct nitrogen-doped hierarchical porous carbon to replace Pt-based catalysts for efficient ORR. Here, nitrogen-doped hierarchical porous carbon (NHPC) was prepared by carbonizing ZTIF-1 and KOH activating. The resultant NHPC4-700 catalyst exhibits a hierarchical porous structure and high specific area (2404 m² g^?1), which promoted the exposure of enough active sites as well as simultaneously enhanced the electron transfer rate, shorten the mass transfer pathway, enhanced ionic conductivity and carbon wetting. The results are capable of remarkably improving the ORR activities of carbon materials. The NHPC4-700 catalyst exhibits a great catalytic performance with onset potential at 0.90 V and limiting current density of ??6.0 mA cm^?2, which is close to commercial Pt/C electrocatalyst. Meanwhile, the NHPC4-700 catalysts had better stability and methanol resistance than that of Pt/C toward ORR. These superior electrochemical properties of the NHPC4-700 catalysts were closely related to their nitrogen-doped hierarchical porous structure and high specific area.

     

Adsorption of methanol on mesoporous SBA-15

The adsorption of methanol on mesoporous SBA-15 has been studied by using Brunauer-Emmett-Teller (BET) surface area analysis, scanning electron microscopy (SEM), Fourier transform infrared (FTIR) spectroscopy, X-ray photoelectron spectroscopy (XPS) and thermogravimetric analysis (TGA). The BET surface area analysis shows decreases of the surface area from 387 to 383 m²/g, pore volume from 0.88 to 0.81 cm³/g and pore diameter from 9.07 to 8.4 nm after methanol adsorption. The appearance of strong IR bands at 2862 and 2964 cm^− 1 due to methyl (-CH₃) symmetric and asymmetric stretching demonstrate the presence of methanol and evidence of successful methanol adsorption. XPS results show increase of carbon and oxygen content on the surface of SBA-15. Thermogravimetric analysis shows that the methanol adsorbed on SBA-15 is stable up to a temperature of 265 °C and that the methanol adlayers decompose between 265 and 588 °C.     

Preparation and characterization of PtRu nanoparticles supported on nitrogen-doped porous carbon for electrooxidation of methanol

N-doped porous carbon nanospheres (PCNs) were prepared by chemical activation of nonporous carbon nanospheres (CNs), which were obtained via carbonization of polypyrrole nanospheres (PNs). The catalysts, PtRu and Pt nanoparticles supported on PCNs and Vulcan XC-72 carbon black, were prepared by ethylene glycol chemical reduction. Transmission electron microscopy, X-ray diffraction, and energy-dispersive X-ray spectroscopy were employed to characterize samples. It was found that PCNs containing N function groups possess a large number of micropores. Uniform and well-dispersed Pt and PtRu particles with narrow particle size distribution were observed. The electrooxidation of liquid methanol on these catalysts was investigated at room temperature by cyclic voltammetry, chronoamperometry and electrochemical impedance spectroscopy (EIS). The results showed that alloy catalyst (Pt(1)Ru(1)/PCN) possessed the highest catalytic activity and better CO tolerance than the other PtRu and Pt-only catalysts; PtRu nanoparticles supported on PCN showed a higher catalytic activity and more stable sustained current than on carbon black XC-72. Compared to commercial Alfa Aesar PtRu catalyst, Pt(1)Ru(1)/PCN reveals an enhanced and durable catalytic activity in methanol oxidation because of the high dispersion of small PtRu nanoparticles and the presence of N species of support PCNs.     

Templated synthesis of nanosized mesoporous carbons

Mesoporous carbon materials formed by nanosized particles have been synthesized by means of a nanocasting technique based on the use of mesostructured silica materials as templates. We found that the modification of the chemical characteristics of the surfactant employed allows mesostructured silica materials with particle sizes <100 nm to be synthesised. The mesoporous carbons obtained from these silica materials retain the structural properties of the silica used as template and consequently they have a particle size in the 20-100 nm range. These carbons exhibit large BET surfaces areas (up to 1300 m² g⁻¹) and high pore volumes (up to 2.5 cm³ g⁻¹), a framework confined porosity made up of uniform mesopores (3.6 nm) and an additional textural porosity arising from the interparticle voids between the sub-micrometric particles. The main advantage of nanometer-sized mesoporous carbons in relation to the micrometer-sized carbons is that they have enhanced mass transfer rates, which is important for processes such as adsorption or catalysis.     

Preparation and gases storage capacities of N-doped porous activated carbon materials derived from mesoporous polymer

In this report, the chemical activation of mesoporous carbon derived from mesoporous polymer is used to prepare N-doped carbon materials with high surface area and narrow pores size distribution. The porous carbons derived from the activation of mesoporous carbon generally possess high surface area up to 2400 m² g⁻¹ and narrow micropores/super-micropore size distribution and exhibit H₂ uptake capacity of up to 4.8 wt% at −196 °C and 20 bar and CO₂ sorption capacity of up to 3.7 mmol g⁻¹ at 25 °C and 1 bar. The measured isosteric heat of adsorption for H₂ sorption is 10 kJ mol⁻¹ and 58 kJ mol⁻¹ for CO₂ sorption, indicating a strong interaction between the carbon surface and adsorbed hydrogen and carbon dioxide respectively.     

One-pot synthetic method to prepare highly N-doped nanoporous carbons for CO2 adsorption

A one-pot synthetic method was used for the preparation of nanoporous carbon containing nitrogen from polypyrrole (PPY) using NaOH as the activated agent. The activation process was carried out under set conditions (NaOH/PPY = 2 and NaOH/PPY = 4) at different temperatures in 600–900 °C for 2 h. The effect of the activation conditions on the pore structure, surface functional groups and CO₂ adsorption capacities of the prepared N-doped activated carbons was examined. The carbon was analyzed by X-ray photoelectron spectroscopy (XPS), N2/77 K full isotherms, scanning electron microscopy (SEM) and transmission electron microscopy (TEM). The CO₂ adsorption capacity of the N-doped activated carbon was measured at 298 K and 1 bar. By dissolving the activation agents, the N-doped activated carbon exhibited high specific surface areas (755–2169 m² g⁻¹) and high pore volumes (0.394–1.591 cm³ g⁻¹). In addition, the N-doped activated carbons contained a high N content at lower activation temperatures (7.05 wt.%). The N-doped activated carbons showed a very high CO₂ adsorption capacity of 177 mg g⁻¹ at 298 K and 1 bar. The CO₂ adsorption capacity was found to be dependent on the microporosity and N contents.     

Fabrication and textural characterization of nanoporous carbon electrodes embedded with CuO nanoparticles for supercapacitors

Abstract

We introduce a novel strategy of fabricating nanoporous carbons loaded with different amounts of CuO nanoparticles via a hard templating approach, using copper-containing mesoporous silica as the template and sucrose as the carbon source. The nature and dispersion of the CuO nanoparticles on the surface of the nanoporous carbons were investigated by x-ray diffraction (XRD), high-resolution scanning electron microscopy (HRSEM) and high-resolution transmission electron microscopy (HRTEM). XRD results reveal that nanoporous carbons with embedded CuO nanoparticles exhibit a well-ordered mesoporous structure, whereas the nitrogen adsorption measurements indicate the presence of excellent textural characteristics such as high surface area, large pore volume and uniform pore size distribution. The amount of CuO nanoparticles in the nanochannels of the nanoporous carbon could be controlled by simply varying the Si/Cu molar ratio of the mesoporous silica template. Morphological characterization by SEM and TEM reveals that high-quality CuO nanoparticles are distributed homogeneously within the nanoporous carbon framework. The supercapacitance behavior of the CuO-loaded nanoporous carbons was investigated. The material with a small amount of CuO in the mesochannels and high surface area affords a maximum specific capacitance of 300 F g^-1 at a 20 mV s^-1 scan rate in an aqueous electrolyte solution. A supercapacitor containing the CuO-loaded nanoporous carbon is highly stable and exhibits a long cycle life with 91% specific capacitance retained after 1000 cycles.     

Synthesis,characterization and comparison of polythiophene–carbon nanocomposite materials as Pt electrocatalyst supports for fuel cell applications

A novel polymer–carbon (PTh–C) nanocomposites containing different percentages of polythiophene (10, 20 and 50% (w/w)) and carbon (Vulcan XC-72) was prepared by a facile solution dispersion method and used to support platinum nanoparticles. The effect of using different percentages of polythiophene in nanocomposites and subsequently prepared electrocatalysts was investigated. The resultant electrocatalysts were extensively characterized by physical (X-ray diffraction (XRD) and transmission electron microscopy (TEM)) and electrochemical (cyclic voltammetry (CV)) techniques. The TEM results showed that the fine Pt nanoparticles prepared by ethylene glycol (EG) method were distributed on the surface of the 50% PTh–C nanocomposites successfully. From the XRD patterns, the average size of dispersed Pt nanoparticles with the face-centered cubic (fcc) structure on 50% PTh–C, 20% PTh–C, 10% PTh–C and carbon were about 4.9, 5.2, 5.4 and 6.1 nm, respectively. The conductivity of PTh–C with different percentages of pure PTh was compared with the conductivity of the corresponding support of pure PTh. It is observed that the conductivity of 50% PTh–C nanocomposites is about 600 times higher than that of pure PTh. Finally, CV measurements of hydrogen and methanol oxidations indicated that Pt/50% PTh–C had a higher electrochemical surface area and higher catalytic activity for methanol oxidation reaction compared to other electrocatalysts. These measurements showed that the Pt/50% PTh–C electrocatalyst by the value of 3.85 had higher \(I_{\mathrm{f}}/I_{\mathrm{b}}\) ratio with respect to Pt/10% PTh–C and Pt/20% PTh–C by the values of 2.66 and 2.0, respectively.     

载体表面化学状态对Pt/C催化剂结构及电催化活性的影响

对碳黑进行不同条件的氧化处理得到不同表面化学状态的载体,以甲醛为还原剂,氯铂酸为前驱体,制备Pt/C电催化剂.运用X射线光电子能谱(XPS)、X射线衍射(XRD)、透射电镜(TEM)等分析手段研究碳黑及Pt/C催化剂的化学组成、化学状态、晶体结构及表面形貌,并用循环伏安法(CV)测试Pt/C催化剂对甲醇的电催化氧化.结...     

Preparation of Pt/multiwalled carbon nanotubes modified Au electrodes via Pt–Cu co-electrodeposition/Cu stripping protocol for high-performance electrocatalytic oxidation of methanol

Pt nanoparticles well dispersed on multiwalled carbon nanotubes (MWCNTs) were prepared for high-performance electrocatalytic oxidation of methanol in both acidic and alkaline media via the co-electrodeposition/stripping (CS) protocol, namely, co-electrodeposition of Pt and Cu followed by electrochemical stripping of Cu, as examined by cyclic voltammetry (CV), electrochemical quartz crystal microbalance (EQCM), scanning electron microscopy (SEM), and X-ray diffraction (XRD). The Pt catalyst prepared by the CS protocol on MWCNTs (Pt_cs/MWCNTs/Au) exhibited a specific electrocatalytic activity of 519 and 2210 A g⁻¹ toward cyclic voltammetric electrooxidation (50 mV s⁻¹) of methanol in 0.5 M CH₃OH + 0.5 M H₂SO₄ and 0.5 M CH₃OH + 1.0 M NaOH media, respectively, which are larger than those prepared by conventional electrodeposition from chloroplatinic acid on Au and MWCNTs/Au, as well as that by a CS protocol on Au. The Pt_cs/MWCNTs/Au electrode also possessed the highest stability, which maintained 91% and 90% of its initial catalytic activity after 120-cycle CV in 0.5 M CH₃OH + 0.5 M H₂SO₄ and 0.5 M CH₃OH + 1.0 M NaOH, respectively. The electrode kinetics of methanol oxidation is also briefly discussed. The nanosubstrate-based CS protocol is simple, convenient and efficient, which is expected to find wide applications in film electrochemistry and electrocatalysis.     

PEDOT-PSSA as an alternative support for Pt electrodes in PEFCs

Poly (3,4-ethylenedioxythiophene) (PEDOT) and poly (styrene sulphonic acid) (PSSA) supported platinum (Pt) electrodes for application in polymer electrolyte fuel cells (PEFCs) are reported. PEDOT-PSSA support helps Pt particles to be uniformly distributed on to the electrodes, and facilitates mixed electronic and ionic (H⁺-ion) conduction within the catalyst, ameliorating Pt utilization. The inherent proton conductivity of PEDOT-PSSA composite also helps reducing Nafion content in PEFC electrodes. During prolonged operation of PEFCs, Pt electrodes supported onto PEDOT-PSSA composite exhibit lower corrosion in relation to Pt electrodes supported onto commercially available Vulcan XC-72R carbon. Physical properties of PEDOT- PSSA composite have been characterized by X-ray diffraction, Fourier transform infrared spectroscopy, scanning electron microscopy and transmission electron microscopy. PEFCs with PEDOT-PSSA-supported Pt catalyst electrodes offer a peak power-density of 810 mW cm⁻² at a load current-density of 1800 mA cm⁻² with Nafion content as low as 5 wt.% in the catalyst layer. Accordingly, the present study provides a novel alternative support for platinized PEFC electrodes.     

Synthesis of spheroidal ordered mesoporous carbon materials from silica/P123/butanol composites

Spheroidal ordered mesoporous carbon materials with diameter of 2–10 μm were synthesized by direct carbonization of silica/triblock copolymer P123/butanol composites using P123 and butanol as the structure-directing agents and carbon precursors. The morphologies, structures and pore characteristics of the carbon materials were investigated by scanning and transmission electron microscopes, X-ray diffraction, and nitrogen sorption. It was found that the material possesses a cubic ordered mesoporous structure with Ia3d symmetry. The butanol addition directly affects the carbon morphology and pore structure. When the mass ratio of butanol to P123 is 0.5:1, the product exhibits a perfectly spheroidal morphology with a specific surface area of 1236 m² g⁻¹ and a total pore volume of 1.26 cm³ g⁻¹. The formation mechanism of the spheroidal ordered mesoporous carbon materials is discussed briefly.     

Carbon supported silver (Ag/C) electrocatalysts for alkaline membrane fuel cells

This study reports on the performance of activated carbon supported silver catalyst (Ag/C) as electrocatalyst in an alkaline membrane fuel cell (AMFC), using alkalized poly (styrene ethylene butylene poly styrene) [APSEBS] as the electrolyte membrane. Carbon supported silver catalyst (Ag/C) with different metal loading was synthesized by means of wet impregnation method. The prepared electrocatalyst was characterized by X-ray diffraction pattern (XRD), thermogravimetric analysis (TGA), UV–Visible diffuse reflectance spectra (DRS-UV) and Raman spectroscopy. Surface morphology analysis of the prepared electrocatalyst using scanning electron microscopy (SEM) revealed the heterogeneous distribution of Ag on carbon support. The performance of the prepared electrocatalyst was evaluated with a home made AMFC using a novel anion exchange membrane (APSEBS). A maximum cell voltage and power density of 0.69 V and 109 mW/cm², respectively, was achieved at 60 °C for the home made 10 wt% (Ag/C) cathode catalyst and anion exchange membrane. Further, the prepared electrocatalyst was subjected to cyclic voltammetry studies to evaluate the methanol oxidation for Direct methanol alkaline fuel cell (DMAFC) applications.     

Use of single wall carbon nanohorns in polymeric electrolyte fuel cells

Single wall carbon nanohorns (SWNH), produced by AC arc discharge in air, were used as Pt and PtRu supports in polymer electrolyte membrane fuel cells (PEMFC). These electrocatalysts were compared with equivalent electrocatalysts supported on commercial carbon back. The SWNH were characterized by differential thermal analysis (DTA), TEM, SEM, and XRD. The produced SWNH were 84.5 wt% pure, containing 3 wt% of amorphous carbon and 12.5 wt% of graphitic carbon. SWNH were used as electrocatalyst supports and tested in the electrodes of two types of polymer electrolyte fuel cells: H₂-fed PEMFC and direct methanol fuel cells (DMFC). The electrocatalyst nanoparticles anchored on both carbon supports were ca. 2.5 nm in diameter obtained by employing ethylene glycol as the reducing agent. The use of SWNH showed catalytic activities 60% higher than using carbon black as the electrocatalyst support in both types of fuel cells.     

High Density Single Fe Atoms on Mesoporous N-Doped Carbons: Noble Metal-Free Electrocatalysts for Oxygen Reduction Reaction in Acidic and Alkaline Media

It remains a challenge to develop efficient noble metal-free electrocatalysts for the oxygen reduction reaction (ORR) in various renewable energy systems. Single atom catalysts have recently drawn great attention as promising candidates both due to their high activity and their utmost atom utilization for electrocatalytic ORR. Herein, the synthesis of an efficient ORR electrocatalyst that is composed of N-doped mesoporous carbon and a high density (4.05 wt%) of single Fe atoms via pyrolysis Fe-conjugated polymer is reported. Benefiting from the abundant atomic Fe–N₄ sites on its conductive, mesoporous carbon structures, this material exhibits an excellent electrocatalytic activity for ORR, with positive onset potentials of 0.93 and 0.98 V in acidic and alkaline media, respectively. Its electrocatalytic performance for ORR is also comparable to that of Pt/C (20 wt%) in both media. Furthermore, it electrocatalyzes the reaction almost fully to H₂O (or barely to H₂O₂). Additionally, it is durable and tolerates the methanol crossover reaction well. Furthermore, a proton exchange membrane fuel cell and a zinc–air battery assembled using it on their cathode deliver high maximum power densities (320 and 91 mW cm⁻², respectively). Density functional theory calculation reveals that the material's decent electrocatalytic performance for ORR is due to its atomically dispersed Fe–N₄ sites.