Nitrogen-doped graphene nanosheets as high efficient catalysts for oxygen reduction reaction

It is of great significance in exploring alternative catalysts to platinum (Pt)-based materials for oxygen reduction reaction (ORR),because this reaction is invariably involved in various fuel cells and metal-air batteries.We herein reported the nitrogen doped graphene nanosheets (NGNSs) with pore volume of as high as 3.42 m 3 /g and investigated their potential application as ORR catalysts,it was demonstrated the NGNSs featured high activity,improved kinetics and excellent long-term stability for ORR.The NGNSs were successfully used as cathode catalysts of microbial fuel cells (MFCs) and performed even better than the commercial Pt/C (Pt 10%) catalysts at the maximum power output.     

Reduction of Pt Usage in Fuel Cell Electrocatalysts Using Carbon Nanotubes and Non-Pt Metals

The high-priced and limited Pt constitutes a high barrier to commercialization of fuel cells. Pt is essential for the electrode catalyst of polymer electrolyte fuel cells （PEFCs）. A reduction in Pt usage is one of the key requirements for the commercialization of fuel cells for use in everyday life, because of its high price and limited availability, and the difficulty of finding suitable substitutes. Non-Pt fuel cell catalysts will decrease the demand for Pt by PEFCs, enabling more Pt to be available for use in other essential products, and make fuel cells more popular. The cheaper Mo2C is known to possess similar catalytic activities and electronic structures to Pt. Carbon black （CB） is widely used as the support for Pt nanoparticles. However,     

Synergistic effect between ceria and tungsten oxide on WO3–CeO2–TiO2 catalysts for NH3-SCR reaction

WO3–CeO2–TiO2 catalysts for NO (nitrogen monoxide) reduction by ammonia were prepared by a sol–gel method. The catalysts were characterized by BET, XRD, Raman, NH3/NO adsorption and H2-TPR to investigate the relationships among the catalyst composition, structure, redox property, acidity and deNOx activity. WO3–CeO2–TiO2 catalysts show a high activity in a broad temperature range of 200–480 1C. The low-temperature activity of catalysts is sensitive to the catalyst composition especially under low-O2-content atmospheres. It may be related to the synergistic effect between CeOx and WOx in the catalysts. On one hand, the interaction between ceria and tungsten oxide promotes the activation of gaseous oxygen to compensate the lattice oxygen consumed in NH3-SCR (selective catalytic reduction) reaction at low temperatures. Meanwhile, the Br?nsted acid sites mainly arise from tungsten oxides, Lewis acid sites mainly arise from ceria. Both of the Br?nsted and Lewis acid sites facilitate the adsorption of NH3 on catalysts and improve the stability of the adsorbed ammonia species, which are beneficial to the NH3-SCR reaction.     

Nano-gold Catalyst for Direct Alcohol Fuel Cells

1 Results Direct alcohol fuel cells have been regarded as attractive power sources for portable electric devices. One of the major roadblocks to the implementation of direct alcohol fuel cells is the exploration of the anode catalyst that can electrochemically oxidize alcohols at lower potentials. Carbon-monoxide (CO) produced through alcohol oxidation deteriorates catalytic activity of Pt, and therefore, the high tolerance for CO poisoning is an important issue to attain high voltage from direct alcohol fuel cells. To fabricate CO tolerant anode catalysts, we have focused on gold nanoparticles that have attracted much attention since Haruta and his coworkers found the gaseous CO oxidation by the nanoparticles even below 0 ℃ for the first time[1].     

烧结铁矿中FeO含量对其在富氢高炉中还原行为的影响

Japan started the national project “COURSE 50” for CO₂ reduction in the 2000s. This project aimed to establish novel technologies to reduce CO₂ emissions with partially utilization of hydrogen in blast furnace-based ironmaking by 30% by around 2030 and use it for practical applications by 2050. The idea is that instead of coke, hydrogen is used as the reducing agent, leading to lower fossil fuel consumption in the process. It has been reported that the reduction behavior of hematite, magnetite, calcium ferrite, and slag in the sinter is different, and it is also considerably influenced by the sinter morphology. This study aimed to investigate the reduction behavior of sinters in hydrogen enriched blast furnace with different mineral morphologies in CO–CO₂–H₂ mixed gas. As an experimental sample, two sinter samples with significantly different hematite and magnetite ratios were prepared to compare their reduction behaviors. The reduction of wustite to iron was carried out at 1000, 900, and 800°C in a CO–CO₂–H₂ atmosphere for the mineral morphology-controlled sinter, and the following findings were obtained. The reduction rate of smaller amount of FeO led to faster increase of the reduction rate curve at the initial stage of reduction. Macro-observations of reduced samples showed that the reaction proceeded from the outer periphery of the sample toward the inside, and a reaction interface was observed where reduced iron and wustite coexisted. Micro-observations revealed three layers, namely, wustite single phase in the center zone of the sample, iron single phase in the outer periphery zone of the sample, and iron oxide-derived wustite FeO and iron, or calcium ferrite-derived wustite 'FeO' and iron in the reaction interface zone. A two-interface unreacted core model was successfully applied for the kinetic analysis of the reduction reaction, and obtained temperature dependent expressions of the chemical reaction coefficients from each mineral phases.     

Pt-induced electrochemical growth of ZnO rods onto reduced graphene oxide for enhanced photodegradation performance

Photodegradation of organic pollutants over semiconductor catalysts is considered to be a viable method for wastewater treatment.Of the different semiconductor photocatalysts,ZnO has been widely used for the photodegradation of organic pollutants.Meanwhile,graphene is being actively investigated as a cocatalyst for such processes.The high carrier transport rate of graphene can favor the transfer of photoexcited electrons,while the increased specific surface area provides adsorption sites for the organic effluent molecules,thereby improving overall photocatalytic activity.Therefore,in this study,Pt–ZnO–reduced graphene oxide(RGO)rods with different RGO contents are synthesize during a novel Pt-induced electrochemical method,where ZnjZnO acts as the anode and PtjH2OjH2acts as the cathode.The photocatalytic degradation activity of the Pt–ZnO–RGO rods is remarkably improved under UV–visible light irradiation,with the optimum loading RGO content of 1 wt%.     

PtCo alloy nanoparticles supported on graphene nanosheets with high performance for methanol oxidation

PtCo alloy nanoparticles are deposited onto graphene sheets through a facile and reproducible hydrothermal method.During the hydrothermal reaction,the reduction of graphene oxide and PtCo alloy nanoparticles loading can be achieved.X-ray diffraction (XRD) analyses reveal a good crystallinity of the supported Pt nanoparticles in the composites and the formation of PtCo alloy.X-ray photoelectron spectra (XPS) results depict that Pt mainly exists in the metallic form,while much of the cobalt is oxidized.Transmission electron microscope (TEM) observations show that the PtCo alloy nanoparticles are uniformly dispersed on graphene nanosheets compared with multiwalled carbon nanotubes (MWNTs).This PtCo-graphene composite exhibits excellent electrocatalytic activity and high poison tolerance toward poisoning species for methanol oxidation reaction,far outperforming the Pt-graphene or PtCo-MWNTs composites with the same feeding ratio of Pt/carbon.     

Proton-conducting Membranes Based on PVA-PAMPS Semi-interpenetrating Polymer Networks for Low Temperature Direct Methanol Fuel Cells

In direct methanol fuel cells （DMFCs） the methanol crossover from anode to cathode through the polymer electrolyte membrane is a major isue, because this not only causes loss of fuel, but also reduces the performance at the cathode due to the mixed reaction of methanol oxidation with oxygen reduction reaction. Membranes that show high proton conductivity, and at the same time, low methanol permeability are strongly desired but difficult to attain, because of trade-off relations between these parameters. We here report a new type of cost-effective polymer blend membranes based on chemically cross-linked poly（vinyl alcohol） （PVA） and 2-acrylamido-2-methyl-1-propanesulfonic acid （PAMPS） which is called semi-interpenetrating polymer networks （semi-IPNs）.     

Highly efficient anode catalyst with a Ni@Pd Pt core–shell nanostructure for methanol electrooxidation in alkaline media

To enhance the electrocatalytic activity of anode catalysts used in alkaline-media direct methanol fuel cells(DMFCs), a Ni@Pd Pt electrocatalyst was successfully prepared using a three-phase-transfer method. The Ni@Pd Pt electrocatalyst was characterized by X-ray diffraction(XRD), X-ray photoelectron spectroscopy(XPS), transmission electron microscopy(TEM), and high-resolution TEM(HRTEM) techniques. The experimental results indicate that the average particle size of the core–shell-structured Ni@Pd Pt electrocatalyst is approximately 5.6 nm. The Ni@Pd Pt electrocatalyst exhibits a catalytic activity 3.36 times greater than that of Pd Pt alloys for methanol oxidation in alkaline media. The developed Ni@Pd Pt electrocatalyst offers a promising alternative as a highly electrocatalytically active anode catalyst for alkaline DMFCs.     

Comparison of corrosion and oxygen evolution behaviors between cast and rolled Pb–Ag–Nd anodes

The corrosion and oxygen evolution behaviors of cast and rolled Pb–Ag–Nd anodes were investigated by metalloscopy, environmental scanning electron microscopy, X-ray diffraction analysis, and various electrochemical measurements. The rolled anode exhibits fewer interdendritic boundaries and a dispersed distribution of Pb–Ag eutectic mixtures and Nd-rich phases in its cross-section. This feature inhibits rapid interdendritic corrosion into the metallic substrate along the interdendritic boundary network. In addition, the anodic layer formed on the rolled anode is more stable toward the electrolyte than that formed on the cast anode, reducing the corrosion of the metallic substrate during current interruption. Hence, the rolled anode has a higher corrosion resistance than the cast anode. However, the rolled anode exhibits a slightly higher anodic potential than the cast anode after 72 h of galvanostatic polarization, consistent with the larger charge transfer resistance. This larger charge transfer resistance may result from the oxygen-evolution reactive sites being blocked by the adsorption of more intermediates and oxygen species at the anodic layer/electrolyte interfaces of the rolled anode than at the interfaces of cast anode.     

氧化铈纳米粒子的制备及其生物应用进展

由于铈离子可以在Ce~(3+)和Ce~(4+)之间可逆转换,以及氧空位的存在,氧化铈(CeO_(2-x),x=0～0.5)纳米粒子具有优异的催化特性,作为一种用途广泛的稀土氧化物得到了广泛的关注.Ce原子能够快速而大幅度地调整其电子结构(如产生氧空位或缺陷),以最佳的结构适应其周围环境,具有多种酶类活性(包括超氧化物氧化酶、过氧化氢酶和氧化酶等),可以清除体内产生的各种毒性活性氧.氧化铈在生物分析、生物医学、药物传递和生物支架等生物领域展现出了良好的应用前景.综述了氧化铈的制备方法及其在生物领域的应用进展.     

Highly stable N-containing polymer-based Fe/Nx/C electrocatalyst for alkaline anion exchange membrane fuel cell applications

A cost-effective electrocatalyst with high activity and stability was developed. The Fe-Nx and pyridinic-N active sites were embedded in nitrogen-doped mesoporous carbon nanomaterial by carbonization at high temperature. The electrocatalyst exhibited excellent electrochemical performance for the oxygen reduction reaction, with high onset potential and half-wave potential values (E_onset = 1.10 ?V and E_1/2 ?= ?0.944 ?V) than 20 ?wt % Pt/C catalyst (1.04 and 0.910 ?V). The mass activity of the Schiff base network (SNW) based SNW-Fe/N/C@800° electrocatalyst (0.64 ?mA ?mg^?1 @ 1 ?V) reached about half of the commercial Pt/C electrocatalyst (1.35 ?mA ?mg^?1 @ 1 ?V). The electrocatalyst followed the 4-electron transfer mechanism due to very low hydrogen peroxide yield (H₂O₂ ?< ?1.5%) was obtained. In addition, this electrocatalyst with dual active sites showed high stability during cyclic voltammetry and chronoamperometry measurements. More importantly, the electrocatalyst also demonstrated the power density of 266 ?mW ?cm^?2 in the alkaline anions exchange membrane fuel cell (AEMFC) test, indicating its prospective application for fuel cells.     

Adsorption and reaction of CO and O2 on the Ag/Pt(110) surface studied by photoemission electron microscopy

The Ag/Pt(110) model catalyst was prepared by evaporating silver on Pt(110). Adsorption and reaction of CO and O₂ on Ag/Pt(110) surface were studied in situ by photoemission electron microscopy (PEEM) during the pressure range of 10^-5——10^-2 Pa at 480 K. The Ag/Pt(110) surface consisted of Pt(110), AgPt interface and Ag area after annealing at 500 K. The dosing pressure of CO and O₂ had a larger influence on their adsorption on the Ag area than on the Pt(110) and AgPt interface. Small Pt clusters formed on the Ag area and AgPt interface, which had a stronger ability to adsorb CO than Pt(110) terrace. The existence of Ag had an obvious influence on the kinetic of CO oxidation on Pt(110). No pattern was observed on the AgPt interface under the same condition when the formation of reaction-diffusion waves occurred on Pt(110).     

Microstru cture and oxygen storage capacity of Sr-modified Pt/CeO2 –ZrO2catalysts

Strontium was introduced into CeO2–ZrO2 mixed oxides (CZ) by doping and impreg-nation metho ds, and then Pt was impregnated on the Sr-modifie d CZ to obtain the catalysts. X-ray diffraction (XRD), X-photon spectra (XPS), high-resolution transmission electronic microscopy (HRTEM) and H2 temperature programmed reduction (TPR) were carried out to characterize the micro-structure and reducibility of catalysts. The oxygen storage capacity (OSC) was evaluated with CO serving as probe gas. The results showed that the incorporation of Sr₂₊ in the lattice of CZ could promote the OSC properties by increasing the structure defects and enhancing the diffusion rate of oxygen from bulk to surface. For the Sr-impregnated sample, the strong metal–support interaction (SMSI) between Pt and CZ was interrupted, since Sr covered parti al surface Ce species. Such interruption retarded the back-spillover effect occurring at the Pt/Ce interface at low temperature, resulting in the loss of OSC. Meanwhile, it was found that a part of impregnated Sr₂₊ could partially diffuse from the surface to the inner atomic layers of CZ and partially incorporated in the lattice during the calcination. The OSC performance of Sr-impregnated sample therefore climbed remarkably with the rise of temperature.     

Role of support in photothermal carbon dioxide hydrogenation catalysed by Ni/CexTiyO2

Nickel was supported on varied ratios of ceria-titania mixed oxides(Ni/Ce_xTi_yO_2) to evaluate the role the support plays in photothermal carbon dioxide hydrogenation to produce methane. In a batch photothermal reactor system, Ni/CeO_2 achieved the highest conversion rate, reaching a conversion of 93% in approximately60–90 min. To decouple the influence of light and heat, the CO_2 hydrogenation was examined in an in-house designed photothermal reactor, whereby heat can be applied externally. Decoupling experiments revealed that heat from the thermalisation by light was the main driving force for the reaction. In addition, the conversion and temperature profile of the different catalysts revealed that the catalyst performance was governed by catalyst reducibility. H_2-TPR analyses showed that the Ni became more readily reducible with increasing Ce O_2 content,suggesting that the oxide plays a role in activating the Ni. The reduction temperature of the nickel catalyst(following a reduction and passivation process) was below 200 °C, which meant that the inherent heating temperature of the photothermal reactor was sufficient to initiate Ni/CexTiyO_2 catalyst activity. The exothermic methanation reaction was then able to heat the system further, ultimately reaching a temperature of 285 °C. The ancillary rise in temperature promotes further nickel reduction and methane formation, leading to a "snow-ball"effect. The findings demonstrate that, to achieve a "snow-ball" effect in a photothermal system, designing a catalyst which is easy to reduce, active for CO_2 hydrogenation, and capable of converting light to heat for its initial activation is critical.     

Influence of interactions between chromium and cerium on catalytic performances of CrO_x–CeO_2/Ti-PILC catalysts for deep oxidation of n-butylamine

A series of CrOx-CeO2/Ti-PILC （PILC is pillared interlayered clay） catalysts for n-butylamine oxidation were prepared using an impregnation method, and the structures, surface acidity distributions, and redox properties of the catalysts were characterized using X-ray diffraction, X-ray photoelectron spectroscopy, transmission electron microscopy, H2 temperature-programmed reduction, and NH3 temperature-programmed desorption. The results show that addition of an appropriate amount of CeO2 enhances the interactions between Cr and Ce, and this increases the acid strength and mobility of active oxygen species on the cata- lyst. 8CrCe（6：1）/Ti-PILC（12,20） exhibits the best catalytic performance and control of NOx in n-butylamine oxidation.     

Pyrolysis of Iron(III) porphyrin coated Pt/C toward oxygen reduction reaction in acidic medium

Design and synthesis of highly active and durable electrocatalysts toward oxygen reduction reaction (ORR) is of particular importance for proton exchange membrane fuel cells (PEMFCs), yet remains a grand challenge. Herein, we report the deposition of iron (III) porphyrin (FeP) on house-made Pt/C by rotary evaporation of the mixture of FeP and house-made Pt/C dispersed in chloroform, followed by pyrolysis at 650 °C in argon atmosphere. This approach led to the synthesis of new non-precious metal electrocatalyst (NPME)-Pt/C composites (Pt/C–FeP) with an average nanoparticle diameter of 3.1 ± 1.5 nm without aggregation. According to X-ray photoelectron spectroscopy (XPS), the binding energy of Pt 4f_7/2 became larger due to the presence of pyrolyzed FeP. In addition, the electrochemically active surface area (ECSA) of Pt/C–FeP-650 is 65 m²/g less than that of house-made Pt/C (80.2 m²/g). This implies that the pyrolyzed FeP may have partially covered the surface of Pt nanoparticles and thus lowering the ECSA. Interestingly, the mass activity (MA) of Pt/C–FeP turns out to be 349.0 mA/mg_Pt @0.9 V vs. RHE, which is 2.6 times and 1.5 times of house-made Pt/C and commercial Pt/C, respectively. It is speculated that the electronic interaction and possible synergy between Pt and pyrolyzed FeP as NPME might have contributed to the ORR activity improvement despite of partial loss of ECSA. During accelerated durability tests (ADTs), the MA of Pt/C–FeP-650 degrades 64.3% inferior to commercial Pt/C (52.2%). The main reason likely arises from the degradation of pyrolyzed FeP, which is a bottleneck problem confronting NPMEs.     

Microstructure and electrolysis behavior of self-healing Cu-Ni-Fe composite inert anodes for aluminum electrowinning

The microstructure evolution and electrolysis behavior of (Cu₅₂Ni₃₀Fe₁₈)-xNiFe₂O₄ (x=40wt%, 50wt%, 60wt%, and 70wt%) composite inert anodes for aluminum electrowinning were studied. NiFe₂O₄ was synthesized by solid-state reaction at 950℃. The dense anode blocks were prepared by ball-milling followed by sintering under a N₂ atmosphere. The phase evolution of the anodes after sintering was determined by scanning electron microscopy and energy-dispersive X-ray spectroscopy. The results indicate that a substitution reaction between Fe in the alloy phase and Ni in the oxide phase occurs during the sintering process. The samples were also examined as inert anodes for aluminum electrowinning in the low-temperature KF-NaF-AlF₃ molten electrolyte for 24 h. The cell voltage during electrolysis and the corrosion scale on the anodes were analyzed. The results confirm that the scale has a self-repairing function because of the synergistic reaction between the alloy phase with Fe added and the oxide phase. The estimated wear rate of the (Cu₅₂Ni₃₀Fe₁₈)-50NiFe₂O₄ composite anode is 2.02 cm·a-1.     

FeCo-based mesoporous carbon shells modified N-doped porous carbon spheres for oxygen reduction reaction

FeCo-based non-noble metal electrocatalysts (NNMEs) of FeCo/MCS-NPCS was fabricated by immobilization of hemin on mesoporous carbon shells modified N-doped porous carbon spheres (MCS-NPCS). The obtained FeCo/MCS-NPCS exhibits a half-wave potential (E_1/2) of 0.851 ​V versus the reversible hydrogen electrode (vs. RHE) and a limited-diffusion current density (J_L) of 5.45 ​mA ​cm⁻². In addition, FeCo/MCS-NPCS shows comparable oxygen reduction reaction (ORR) performances to 20 ​wt% Pt/C in terms of E_1/2 and J_L and better electrochemical properties, including the methanol tolerance and durability in alkaline solution. Such outstanding electrochemical activities of FeCo/MCS-NPCS can be ascribed to Fe and/or Co-based nitrides and carbides as well as N-doped carbon matrixes modified with mesoporous carbon shells. This research introduces a promising path to design and synthesize highly efficient FeCo–N–C electrocatalysts towards ORR.