Present status and future prospect of design of Pt–cerium oxide electrodes for fuel cell applications

In the research field of proton exchange membrane fuel cells, the design of electrocatalytic activities on Pt-oxide promoter in the anode side has attracted attention for improvement of CO tolerance of Pt in anode side and a lowering of large over-potential loss of the oxygen reduction reaction on the cathode in the fuel cells. In the Pt-oxide promoter series, Pt–CeOx/C is one of the unique systems. It is because the unique behavior of CeOx such as electrochemical redox reaction between Ce3t and Ce4t in the anodic and cathodic reactions of fuel cell is observed. The present short review gives an overview of the recent works for improvement of the CO tolerance of Pt in the Pt–CeOx/C anodes and enhancement of the oxygen reduction reaction activity on Pt in the Pt–CeOx/C cathodes for fuel cell application. To show the design paradigm for fabrication of high quality Pt–CeOx/C electrodes, the authors re-introduced parts of our research results to highlight the important role of interface structure of Pt–CeOx based on the ultimate analysis results. The usefulness of the combined approach of microanalysis and the processing route design is presented.     

Magnetic property and interface structure of Ta/NiO/NiFe/Ta

Ta/NiO/NiFe/Ta multilayers, utilizing Ta as buffer layer, were prepared by rf reactive and dc magnetron sputtering. The exchange coupling field between NiO and NiFe reached a maximum value of 9.6×10³ A/m at a NiO film thickness of 50 nm. The composition and chemical states at interface region of Ta/NiO/Ta were studied by using the X-ray photoelectron spectroscopy (XPS) and peak decomp- osition technique. The results show that there is an “inter- mixing layer” at the Ta/NiO (and NiO/Ta) interface due to a thermodynamically favorable reaction 2Ta + 5NiO = 5Ni + Ta₂O₅. This interface reaction has a great effect on exchange coupling. The thickness of Ni+NiO estimated by XPS depth- profiles is about 8—10 nm.     

Structure and electrochemical properties of LiLaxMn2-xO4 cathode material by the ultrasonic-assisted sol-gel method

Powders of spinel LiLa_xMn_2—xO₄ were successfully synthesized by the ultrasonic-assisted sol-gel (UASG) method. The structure and properties of LiLa_xMn_2—xO₄ were examined by X-ray diffraction (XRD), Fourier transform infrared (FT-IR) spectroscopy, scanning electronic microscopy (SEM), galvanostatic charge-discharge test, and cyclic voltammetry (CV). XRD results show that the La³⁺ can partially replace Mn³⁺ in the spinel and the doped materials with La³⁺ have a larger lattice constant compared with pristine LiMn₂O₄. FT-IR indicates that the absorption peak of Mn³⁺−O and Mn⁴⁺− O bonds has a red and blue shift with the increase of doping lanthanum in LiLa_xMn_2—xO₄, respectively. The charge-discharge test exhibits that the initial discharge capacity of LiLa_xMn_2—xO₄ drops off, and the capacity retention increases gradually at C/5 discharge rate with the increase of doping lanthanum, and LiLa_0.01Mn_1.99O₄ has a higher discharge capacity and a better cycling performance at 1C discharge rate. CV reveals that the doping La³⁺ is beneficial to the reversible extraction and intercalation of Li⁺ ions.     

Effects of substrate temperature and ambient oxygen pressure on growth of Ba(Fe1/2Nb1/2)O3 thin films by pulsed laser deposition

Ba(Fe1/2Nb1/2)O3 thin films were grown on Pt/TiO2/SiO2/Si substrates with pulsed laser deposition (PLD) at temperatures ranging from 823 to 923 K with the varied ambient oxygen pressure. X-ray diffraction (XRD) data confirmed the single phase of polycrystalline Ba(Fe1/2Nb1/2)O3 thin films. The effects of substrate temperature and ambient oxygen pressure on the surface morphologies of the thin films were investigated by atomic force microscopy (AFM) and the growth dynamics of thin films was discussed. Larger grains and denser surface morphologies were observed with increasing substrate temperature. While finer grains were produced with increasing ambient oxygen pressure due to more frequent collisions between the ejected species and ambient oxygen molecules. The influence of the substrate temperature and ambient oxygen pressure on the dielectric properties was also discussed. Improved dielectric constant and decreased dielectric loss was observed for the thin film deposited at evaluated temperature.     

Preparation and characterization of LiAlxMn2-xO4 for a supercapacitor in aqueous electrolyte

LiAl_xMn_2—xO₄ (0≤x≤0.5) was synthesized by high temperature solid-state reaction. The structure and morphology of LiAl_xMn_2—xO₄ were investigated by X-ray diffraction and scanning electron microscopy (SEM). The results indicate that all samples show spinel phase. The polyhedral particles turn to club-shaped, then change to small spherical, and finally become agglomerates with increasing Al content. The supercapacitive performances of LiAl_xMn_2—xO₄ were studied by means of galvanostatic charge-discharge, cyclic voltammetry, and alternating current (AC) impedance in 2 mol·L⁻¹ (NH₄)₂SO₄ aqueous solution. The results show that LiAl_xMn_2—xO₄ represents rectangular shape performance in the potential range of 0-1 V. The capacity and cycle performance can be improved by doping Al. The composition of x=0.1 has the maximum special capacitance of 160 F·g⁻¹, which is 1.37 times that of LiMn₂O₄ electrode. The capacitance loss of LiAl_xMn_2—xO₄ with x=0.1 is only about 14% after 100 cycles.     

纳米Pt/Graphene复合电极的制备及对甲醇电催化性能的影响

采用一步还原法制备直接甲醇燃料电池纳米Pt/graphene (Pt/G)阳极. XRD和SEM表征表明Pt纳米均匀分散于石墨烯表面.循环伏安和计时电流的电化学测定结果表明:复合纳米Pt/G的催化活性和稳定性优于纯铂;采用计时电量法测定298 K时甲醇在硫酸溶液中扩散系数为1.37×10-9 cm2·s-1,以及在不同阶跃电位下甲醇催化氧化反应速率常数k_f.      

Structural and electrical properties of HCl-polyaniline-Ag composites synthesized by polymerization using Ag-coated (NH4)2S2O8 powder

Ag nanoparticles were sputter-deposited on ammonium persulfate ((NH₄)₂S₂O₈) powder to obtain (NH₄)₂S₂O₈-Ag powder, which was used to synthesize the HCl-doped polyaniline-Ag (HCl-PANI-Ag) composite via a polymerization procedure. The Ag nanoparticles were dispersed in the HCl-PANI matrix, and their sizes mainly ranged from 3 to 6 nm. The Ag nanoparticles did not affect the structure of emeraldine salt in the composite, and they increased the ordered crystalline regions in the HCl-PANI matrix. The HCl-PANI-Ag composite had a conductivity of (6.8 ±0.1) S/cm, which is about four times larger than that of the HCl-PANI. The charge transport mechanism in the composite is explained by the three-dimensional Mott variable-range hopping (3D-Mott-VRH).     

Preparation and properties of the SmOx/Rh(100) model surface

The preparation of SmO_x/Rh(100) and CO adsorption on this model surface have been investigated with Auger electron spectroscopy (AES), X-ray photoelectron spectroscopy (XPS) and temperature programmed desorption spectroscopy (TDS). The oxygen adsorption on the SmRh alloy surface leads to the aggregation of Sm on the surface. The thermal treatment of this oxidized surface induces the further agglomeration of SmO_x on the Rh(100) surface. Compared with CO TDS on the clean Rh(100) surface, three additional CO desorption peaks can be observed at 176, 331 and 600 K on the SmO_x/Rh(100) surface. The CO desorption peak at 176 K may originate from CO adsorbed on SmO_x islands, while the appearance of the CO adsorption peaks at 331 and 600 K, depending on the oxidation state of Sm, is attributed to CO species located at the interface of SmO_x/Rh(100).     

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.     

高温水热法合成系列介孔氧化铝负载铂催化

采用高温水热法制备稳定、 高度晶化的介孔氧化铝材料(M-Al₂O₃-n), 通过异丙醇铝前驱体与聚四乙烯基吡啶(P4VP)模板间的酸碱自组装实现材料介孔结构的构筑, 再经高温水热处理（180 ℃）实现孔壁的晶化, 并通过担载少量的铂活性组分研究其在催化完全燃烧苯中的性能. 结果表明: M-Al₂O₃-n具有高度晶化的孔壁结构和典型的γ-Al₂O₃晶型; M-Al₂O₃-n具有较大的比表面积（335 m²/g）、 孔容(1.36 cm³/g)和均一的孔径分布（16.1 nm）; M-Al₂O₃-n具有粗糙的表面结构及丰富的纳米多孔结构; 该材料负载少量的铂（质量分数为03%）活性组分得到的新型催化材料在较温和的条件下即可将苯类VOCs完全催化燃烧.     

High-pressure synthesis and properties of CeO2-ZrO2 solid solution

Using nanoparticles of CeO₂ and ZrO₂ prepared by the chemical precipitation method as starting materials, the singlephase cubic Ce_0.5Zr_0.5O₂ solid solution (cCe_0.5Zr_0.5O₂) has been synthesized under 3.1 GPa at 1073 K for the first time. The structure of the c-Ce_0.5Zr_0.5O₂ has not been changed before and after annealing at 773 K for 1 h. Only an unknown EPR signal (g =1.990) has been observed in the c-Ce_0.5Zr_0.5O₂ and not varied after annealing at 773 K for 1 h, which exhibited that there exists no Ce³⁺ in the c-Ce_0.5Zr_0.5O₂ and the Ce⁴⁺ has not been reduced into Ce³⁺ after annealing. The transport mechanism is ionic for the c-Ce_0.5Zr_0.5O₂. The bulk conductivity (σ =1.2 ×10⁻⁵ S/cm at 823 K, σ=2.1 × 10⁻³ S/cm at 1123 K) is the same as that of CeO₂, but smaller than that of Y₂O₃-stabilized ZrO₂. A marked curvature at T = 823 K has been observed in the Arrhenius plot of the bulk conductivity. The activation energy below 823 K is lower than that above 823 K, and the reason has been discussed.     

Direct electrochemistry and electrocatalysis of horseradish peroxidase in MnO2 nanosheet film

A novel material MnO2 nanosheet has been used as the support matrix for the immobilization of horseradish peroxidase （HRP）. HRP entrapped in MnO2 nanosheet film exhibits facile direct electron transfer with the electron transfer rate constant of 6.86 s^-1. The HRP/MnO2 nanosheet film gives a reversible redox couple with the apparent formal peak potential （E^0＇） of -0.315 V （vs. Ag/AgCl） in pH 6.5 phosphate buffer solution （PBS）. The formal potential E^0＇ of HRP shifts linearly with pH with a slope of -53.75 mV.pH^-1, denoting that an electron transfer accompanies single-proton transportation. The immobilized HRP shows an electrocatslytic activity to the reduction of H2O2. The response time of the biosensor for H2O2 is less than 3 s, and the detection limit is 0.21 μmol · L^-1 based on signal/noise = 3.     

ZrO_2-supported α-MnO_2:Improving low-temperature activity and stability for catalytic oxidation of methane

The single phaseα-Mn O_2and in-situ supportedα-Mn O_2/Zr O_2with different ratios of Mn/Zr were synthesized by one-pot hydrothermal method.They showed superior activity for catalytic oxidation of methane and even better than that of 1%Pt/Al_2O_3.The T_(50)of Mn O_2/Zr O_2catalysts with different ratios of Mn/Zr were located in the range of 315–335°C at a WHSV of 90 L g~(-1)h~(-1),whereas that of Pt/Al_2O_3was 380°C.After sulfur ageing,the Mn O_2/Zr O_2catalysts with Mn/Zr ratio of 2:1(2Mn O_2/1Zr O_2)and 1:1(1Mn O_2/1Zr O_2)exhibited satisfying sulfur resistance in comparison to the pure Mn O_2.The 2Mn O_2/1Zr O_2catalyst also showed acceptable catalytic stability,and the addition of 10 vol%CO_2had no obvious negative effect on its stability,whereas the addition of2.6 vol%H_2O caused slight but reversible decreasing methane oxidative activity.     

用于邻苯基苯酚合成的Pt-K/Al2O3脱氢催化剂(Ⅱ):催化剂失活机制

采用热重-差热分析(TG-DTA)、元素分析、氢氧滴定(HOT)、扫描电镜能谱分析(SEM-EDS)、透射电镜(TEM)等对Pt-K催化剂可能的失活机制进行研究。结果表明:积碳并非Pt-K催化剂失活的主要原因;脱氢催化剂上铂颗粒的尺寸在运转过程中没有明显的增大,即铂中心烧结也不是催化剂失活的主要原因;Pt-K催化剂在运转过程中铂分散度明显下降而且无法通过再生恢复;Pt-K/Al2O3催化剂的失活极有可能源自催化剂运转过程中钾物种对铂中心的过度覆盖作用。     

Ag沉积Bi12O17Cl2半导体制备及光催化活性研究

采用光原位还原法制备了一系列Ag沉积的氯氧化铋(Ag/Bi₁₂O₁₇Cl₂)二元复合半导体材料,并对其进行表征。X射线光电子能谱分析证实了样品中存在Ag单质,由于Ag颗粒的局部表面等离子体共振效应使紫外可见漫反射光谱图中可见光吸收能力明显增强,扫描电子显微镜图表明制备的材料具有纳米片堆积形成的三维立体形貌。与纯Bi₁₂O₁₇Cl₂样品相比,复合材料可见光照射下对甲苯醇的光催化选择性氧化性能明显增强,这主要与复合材料中形成了金属−半导体异质结以及Ag的等离子体共振效应相关。     

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.     

Dissolution and diffusion of TiO2 in the CaO-Al2O3-SiO2 slag

The dissolution of TiO2 in the CaO-Al2O3-SiO2 slag under static conditions was studied in the temperature range from 1643 K to 1703 K. After TiO2 dissolved, the microstructure of the interface between TiO2 and the slag was observed by scanning electron microscopy, and the concentration profiles of Ti4＋and other ions across the TiO2/slag interfaces were analyzed by energy-dispersive X-ray spectroscopy. On the basis of these results, the dissolution behavior of TiO2 was evaluated, and the diffusivity of Ti4＋in the bulk slag was estimated. Ac-cording to the Stokes-Einstein relation, the viscosity calculated by a previously reported model gave a diffusivity of Ti4＋ions greater than that estimated by the concentration profiles of Ti4＋ions. The mechanism of TiO2 dissolution in the CaO-Al2O3-SiO2 slag is discussed in de-tail.     

The v-v energy transfer of highly vibrationally excited states (I)

The relaxation of the highly vibrationally excited CO (v = 1–8) by CO₂ is studied by timeresolved Fourier transform infrared emission spectroscopy (TR FTIR). 193 nm laser photolysis of the mixture of CHBr₃ with O₂ generates the highly vibrationally excited CO(v) molecules. TR FTIR records the intense infrared emission of CO(v→v-1). The vibrational populations of each level of CO(v) have been determined by the method of spectral simulation. Based on the evolution of the time resolved populations and the differential method, 8 energy transfer rate constants of CO(v = 1–8) to CO₂ molecules areobtained: (5.7±0.1), (5.9±0.1), (5.2±0.2), (3.4±0.2), (2.4±0.3), (2.2±0.4), (2.0±0.4) and (1.8±0.6) (10¹⁴ cm³ · molecule⁻¹ · s⁻¹), respectively. A two-channel energy transfer model can explain the feature of the quenching of CO(v) by CO². For the lower vibrational states of CO, the vibrational energy transfers preferentially to the u³ mode of CO² For the higher levels, the major quenching channel changes to the vibrational energy exchange between CO(v→v-1) and the u¹ mode of CO².     

甲醛在Ag(110)面上的非均相氧化

用热脱附谱、低能电子衍射和电子诱导脱附离子角度分布(ESDIAD)研究了甲醛与氧在Ag(110)面上的吸附和反应。结果表明,低温条件下每个吸附态氧原子能稳住几个甲醛分子,其中大部分在220K时以甲醛形式脱附。ESDIAD照片(225K)进一步证明了HCOOH_(a)中间体的存在,该中间体在235K进一步脱氢,在晶体表面上留下较稳定的吸附态甲酸脂(HCOO_(a))。在250K还出现一个水脱附峰和一个较小的甲醛脱附峰。吸附态甲酸脂在395K分解成CO_2和H_2。对反应机理作了探讨。     

A novel bimetallic RuFe nanocluster to enable highly efficient oxygen reduction in zinc-air batteries

Zinc-air batteries (ZABs) have the advantages of high energy density and safety but their large-scale application is hindered by sluggish kinetics of four-electron aqueous O₂ redox reactions. Widely used Ruthenium (Ru)-based catalysts possess intrinsic oxygen evolution catalytic activity but suffer from insufficient oxygen reduction reaction (ORR) performance. Herein, to optimize the ORR activity of Ru-based catalyst, an iron (Fe)-coordinated, bimetallic RuFe cluster is constructed and homogeneously dispersed within nitrogen (N)-doped carbon layers (denoted as RuFe@NC). Benefitting from the optimized ORR activity and more active site exposure, the RuFe@NC exhibits superior ORR activity with a half wave potential (E_1/2) of 0.88 ?V higher than that of Pt/C (0.82 ?V). Accordingly, the RuFe@NC-based ZAB outperforms the Pt/C ?+ ?IrO₂-based device, presenting a reduced polarization of 0.7 ?V and an enhanced cycling lifetime of 50 ?h at 10 ?mA ?cm^?2. Moreover, the optimized structural design ultralow Ru loading (0.013 mg_Ru cm^?2) overcomes the cost barriers and demonstrates its high practicality. This bimetallic RuFe nanocluster opens a new way for future design of more efficient and stable catalytic systems.