System size and beam energy effects on probing the high-density behavior of nuclear symmetry energy with pion ratio

Based on the isospin-and momentum-dependent hadronic transport model IBUU04, we have investigated the pi(-)/pi(+) ratio in the following three reactions: Ca-48+Ca-48, Sn-124 +Sn-124 and Au-197+Au-197 with nearly the same isospin asymmetry but different masses, at the bombarding energies from 0.25 to 0.6 A GeV. It is shown that the sensitivity of probing the E-sym (rho) with pi(-)/pi(+) increases with increasing the system size or decreasing the beam energy, showing a correlation to the degree of isospin fractionation. Therefore, with a given isospin asymmetry, heavier system at energies near the pion threshold is preferential to study the behavior Of nuclear symmetry energy at supra-saturation densities.

A New High-Spin Level Scheme of I-128

High-spin states in the odd-odd nucleus I-128 are investigated via the Sn-124(Li-7,3n)I-128 reaction at 28 and 32 MeV beam energies. A new level scheme of I-128 is established up to high-spin states at I-pi = 16, including 48 levels and 72 gamma transitions. The present level scheme is largely different from the one in a recent publication due to identification of several doublet and triplet gamma transitions and their proper placements in the level scheme. The high-spin level structure exhibits no obvious collective properties and is possibly associated with two and multi-quasiparticle configurations.

The Compact Pulsed Hadron Source: A Design Perspective

During the past. decades, large-scale national neutron sources have been developed in Asia, Europe, and North America. Complementing such efforts, compact hadron beam complexes and neutron sources intended to serve primarily universities and industrial institutes have been proposed, and some have recently been established. Responding to the demand in China for pulsed neutron/proton-beam platforms that are dedicated to fundamental and applied research for users in multiple disciplines from materials characterization to hadron therapy and radiography to accelerator-driven sub-critical reactor systems (ADS) for nuclear waste transmutation, we have initiated the construction of a compact, yet expandable, accelerator complex-the Compact Pulsed Hadron Source (CPHS). It consists of an accelerator front-end (a high-intensity ion source, a 3-MeV radio-frequency quadrupole linac (RFQ), and a 13-MeV drift-tube linac (DTL)), a neutron target station (a beryllium target with solid methane and room-temperature water moderators/reflector), and experimental stations for neutron imaging/radiography, small-angle scattering, and proton irradiation. In the future, the CPHS may also serve as an injector to a ring for proton therapy and radiography or as the front end to an ADS test facility. In this paper, we describe the design of the CPHS technical systems and its intended operation.

TRITON-(HE)-H-3 RELATIVE AND DIFFERENTIAL FLOWS AND THE HIGH DENSITY BEHAVIOR OF NUCLEAR SYMMETRY ENERGY

Using a transport model coupled with a phase-space coalescence after-burner we study the triton-He-3 relative and differential transverse flows in semi-central Sn-132 + Sn-124 reactions at a beam energy of 400 MeV/nucleon. We find that the triton-He-3 pairs carry interesting information about the density dependence of the nuclear symmetry energy. The t-He-3 relative flow can be used as a particularly powerful probe of the high-density behavior of the nuclear symmetry energy.

CONSTRAINTS ON THE DENSITY DEPENDENCE OF THE SYMMETRY ENERGY

Collisions involving Sn-112 and Sn-124 nuclei have been calculated with the ImQMD transport model in order to place constraints on the density dependences of the nuclear symmetry energy. Consistent constraints on the symmetry energy at sub-saturation density have been obtained by comparing these transport calculations to measurements of isospin diffusion and to the ratios of neutron and proton spectra. New isospin diffusion results from E/A = 35 MeV are also presented.

金属固体在重离子轰击下发射的特征X射线的能移研究

本论文的实验工作，是在兰州重离子加速器国家实验室完成的。实验中，使用ORTEC公司生产HPGe探测器测量了84MeV的12C4+重离子轰击系列金属箔生成的特征X射线。本论文研究了金属薄靶Ag、Cd、In和Sn产生的特征KX射线的能移现象。实验发现Ag、Cd、In和Sn的Kα1和Kα2X射线没有明显的能移现象，而Kβ1X、Kβ2X射线的能移却有100～200eV。对此，应用经典电磁理论详细地解释了该问题。在多组态Dirac-Fock（MCDF）程序计算的单空穴能移的基础上，分别根据实验中测量的特征KX射线的能移值和“几何”模型研究了重离子轰击下Ag、Cd、In和Sn的L、M壳层的多重电离。另外，在相同的条件下，实验测量的厚靶Au的特征LX射线能移不明显，而薄靶Au的特征LX射线却有1.5keV以上的能移。本文定性解释了该实验现象

重离子碰撞中粒子发射的同位旋效应

本文首先介绍了当前核物理的热点问题之一，放射性核束物理中的对称能密度依赖性问题。讨论了对称能的概念、研究意义、介绍了了重离子碰撞输运模型IBUU04。接下来，文章主要研究的是重离子反应中粒子发射的同位旋效应，从而进一步研究对称能的信息。基于IBUU04输运模型，模拟了Sn的两种同位素124Sn+124Sn和112Sn+112Sn在束流能量为50MeV每核子，碰撞参数为2 fm，4 fm，8 fm 的核反应。利用反应的数据，分析了n/p和双n/p的对称能效应以及碰撞参数的依赖性。结果表明：在大碰撞参数的碰撞中，高能核子的双中质比有很明显的对称能效应。同时，还研究了能量为400MeV/A，Sn的同位素的反应中π介子的产生，π-/π+、双π-/π+ 的对称能效应。文章的结尾，我们讨论了A=3的镜像核t和3He发射的对称能效应及碰撞参数依赖性，t-3He流的对称能效应，t/3He同n/p的发射关联。结果表明：在丰中子反应系统,中心碰撞下t/3He同n/p有着关联;大碰撞参数下t/3He有较好的对称能效应，t-3He相对流和微分流有着较好的对称能效应。最后，我们给出了本文的基本结论，就当前工作中的问题和今后发展的方向做出了的展望

30,35MeV/u 36,40Ar＋112,124Sn反应中热核性质同位旋效应的实验研究

针对①中能反应中同位旋自由度是否达到平衡，②同位旋自由度对几中不同方法测量的核温度是否有影响 这两个基本问题，设计了用30和35MeV/u ~(36,40)Ar轰击~(112,124)Sn反应的实验方案。得到如下结果：对于前角5°处的耗散弹核碎裂产物，丰中子同位素与稳定核的产额比随产物出射动能的增加而减小，而丰质子子同位素与稳定核的产额比随动能的增加而增加，呈现明显的剪刀差分布特性。随耗散时间的增大，产物的平均中质比逐渐由弹核的平均中质比向系统的平均中质比过渡。这个结果说明在该反应中，同位旋自由度没有达到完全平衡。而对于20°处的DIC产物，上述剪刀差分布特性变得更不明显，这是同位旋自由度由非平衡向平衡过渡的表现。后角轻粒子的能谱分析表明，初始热核的同位旋会影响斜率核温度的提取，由于丰中子轻粒子~6He在~(40)Ar + ~(112)Sn系统中的蒸发被抑制，相比~(40)Ar + ~(112)Sn而言，其蒸发比较容易发生在衰变链早期，因此提取的温度偏高，同样，丰质子轻粒子~3He的温度在~(40)Ar + ~(112)Sn中略高。但中后角的同位素产额分析表明，反应系统的同位旋对双同位素比核温度几乎没有影响。核温度作为热核的热力学量，是独立于测量方法的，这种不同的方法得出的差异主要来源于同位旋对衰变机制的影响。作为一个尝试，将中高能反应中的熵的提取推广到这个能区，发现两个系统的熵几乎一致。在量子统计模型框架下，考察核温度与熵的关系发现，~(40)Ar + ~(112)Sn反应的挤出时刻密度略高于~(40)Ar + ~(112)Sn。

奇奇核158Ho和124Cs高自旋态的实验研究

奇奇核作为研究准质子和准中子间相互作用的独特侯选核，近年来，人们给予了越来越多的关注。奇奇核高j组态带中观测到的低自旋旋称反转现象(Signature inversion)已成为原子核高自旋态领域中一个十分活跃的研究课题。近十年来，一系列基于二准粒子加转子模型框架的计算结果表明，奇奇核中这两个准粒子之间的相互作用与旋称反转现象的发生密切相关。相对于偶偶核和奇A核，奇奇核的能级结构更复杂一些，实验上对其高自旋态的研究比较困难，这主要体现在实验上所提供的许多奇奇核的能级纲图存在着一定程度的不确定性，例如能级的激发能位置、转动带的组态、自旋和宇称的指定，甚至在纲图结构、级联系列的核素归属等方面都有一些问题。其中，转动带能级自旋的指定直接关系到准粒子能量的劈裂属性(即正常劈裂还是反常劈裂、旋称反转发生在低自旋区还是高自旋区及旋称反转的发生位置等)：自旋的奇偶性定错了，会导致本来是反转的旋称劈裂变成不反转的(反之亦然)；自旋值定错了△I，会导致旋称反转的位置发生相应的漂移。由于实验上奇奇核转动带能级自旋指定的混乱局面，掩盖了旋称反转现象的客观规律，使得相关理论模型的计算结果得不到及时检验。基于激发能系统学分析方法、以顺排角动量相加性为判据，我们曾对A～160轻稀土区的πhl_(11/2)direct X vi_(13/2)转动带(17个核素)和A～130过渡区的πh_(11/2)direct XVh_(ll/2)转动带(20个核素)进行了系统研究，对其中20个核的自旋数据提出质疑、并提出了相应的修正方案，在此基础上总结了两核区旋称反转现象的系统规律。利用激发能系统学方法指定奇奇核转动带的能级自旋，主要遵循以下三点原则：①自旋奇偶性：根据推转壳模型的描述，当准粒子处于优惠态(Favored)时、较非优惠态(Unfavored)具有更大的顺排角动量。这样，通过对转动带中两signature分支系列的i_x大小的比较，可以辅助推断能级自旋的奇偶性；②顺排角动量相加性：在忽略p-n剩余相互作用条件下，奇奇核中总的顺排角动量近似等于相邻奇A核中相应组态带提取的准粒子顺排角动量之和。这样，利用i_x对自旋值比较敏感的特点，可以推断出能级自旋取值的大致范围；③激发能系统性分析：由于集体转动反映大量核子的集体行为，少数核子的改变不会对这种运动产生明显影响，利用转动惯量的组态相关特性，在一组同位素或同中子素系列链中，对应一定内禀结构的转动带，随着质子数或中子数的均匀递增，能级能量应表现光滑的变化趋势(即不发生突变)。这三个方面基于不同角度、相对独立地指定转动带自旋。其结论的统一、往往可以给出正确的自旋数据。然而，必须指出的是：系统学分析过程是一种经验方法，并不具有严格的理论基础，上述的自旋修正以及总结出的旋称反转规律，必须得到实验核谱学测量的支持。基于这一思想，针对两核区，我们分别选择情况较为阿典型的奇奇核~(158)Ho和~(124)Cs进行了集中的实验测量。本论文的主要研究目标就是要建立两核中晕带与低激发态或基态的联系，找出原纲图中错误自旋指定的原因所在，验证系统学结论的有效性，并用旋称反转的实验规律性对理论模型的系统计算结果进行检验。(一)奇奇核~(158)58Ho高自旋态的实验研究在原子能研究院的HI-13串列加速器上，通过~(152)Sm(~(11)B，5nγ)~(158)Ho融合蒸发反应(束流轰击能E_(lab)=60 MeV)、对目标核~(158)Ho的高自旋态进行布居。探测阵列由八个高纯锗探测器构成，为了提高低能射线的收集效率，使用了一个平面型高纯锗探测器。分别进行了激发函数曲线测量、γ-γ-t符合测量和剩余放射性测量。数据反演后，两重符合总记数～120x10~6。实验结果概括如下：1．建立了基态带，组态指定为：{πh_(11/2)[523]7／2-direct Xvh_(9/2)[521]3／2~-}K~π=5~+；2．建立了一个强度仅次于晕带的强耦合带结构(亚晕带：yrare band)。通过转动参数、跃迁几率、顺排角动量、带交叉频率等特征参量的分析，其组态指定为：{πg_(7／2)[404】7／2]~+ direct X vi_(3／2)[651]3／2~+}K~π=5~+。 尽管该带带头附近的结构还不完整，但观测到了带内几条能级退激、分别贯入到晕带和基态带，从而将晕带和亚晕带同基态联系起来，固定了晕带和亚晕带中能级的激发能位置，并通过对这些连接跃迁多极性的分析，指定了两个带中的能级自旋和宇称；3.晕带(πh_(11/2)direct X vi~(13/2))向高自旋端拓展了7条能级，最高自旋态达到26h，激发 能4．9MeV。肯定了原纲图中不确定的617kev跃迁的存在和放置，观测到了反转点(I_(inv.)≈16h)，肯定了系统学研究对该核的自旋修正。基于本实验建立的连接关系，晕带中观测到的最低态(即70.8kev跃迁贯入能级)激发能为207．6kev，而对应该能级，原纲图中激发能为156．9kev。这意味着原能级纲图中，晕带向基态退激途径中漏掉了一个～5lkeV的"能隙"(Energy gap)，自旋差|△I|=3。根据晕带与退激5-同质异能态的跃迁(156．9kev)的快符合关系，该"能隙"至少由两个跃迁构成。该结果否定了原纲图中对晕带带头处理的三种可能性(①70．8kev为连接跃迁，其退激的能级为带头；②70．8kev为带内跃迁，156．9kev、5-同质异能态为带头：⑨70．8kev为带内跃迁，156．9kev、5-同质异能态为带头，但带头附近仍存在尚未观测的跃迁)。不确切的连接关系是过去实验中无法正确指定晕带自旋的原因；4．建立了一个强耦合的转动带结构，其能级间距(跃迁E_γ)随角动量的增加均匀递增，组态指定为{πh_(11/2)[523]7／2~-direct Xvh_(11/2)[505]11／2~-}K~π=9~+；同时，观测到了另一高K激发态退激到该转动带。其内禀结构指定为：{πg_(7／2)[404]7／2~+direct Xvh_(11/2)[505]1 l／2~-}K~π=9~-；5．建立了基于156．9 kev(I~π=5~-、T_(1/2)=29 ns)同质异能态上的转动带，该带观测完整，具有较强耦合的结构特点。其内禀准粒子轨道指定为：{πh_(11/2)[523]_(7／2)~-direct X vd_(3／2)[402]3／2~+}K~π=5~-，与处于较低激发能(67．3 kev)的2~-态(T_(1／2)=27 min．)构成了一对GM伙伴态。否定了过去的实验中把该态指定为{πg_(7/2)~2+direct Xvh_(9/2)[521]3／2~-}K~π=2~-组态；6．观测到了一个基于65．5 kev激发态的转动带，通过理论模型预言的带头激发能及转动参数与实验值的比较、考虑到其较弱的布居强度和很低的顺排角动量、以及较强耦合的结构特点， 其组态指定为： {πd~(5／2)[402]5／2~direct X vh_(9／2)[521]3／2~-}K~π=4~-。这一结果肯定了过去放射性测量中对处于较高激发能(139．2 kev)、T_(1／2)=1．85 ns、I~π=1~-激发态的讨论，即二者构成了一对GM伙伴态；7．建立了基于{πh_(11／2)[523]7／2~-direct X v_(7／2)[523]5／2~-}K~π=6~+激发态的强耦合转动带结构，其带头激发能为450．1 kev，与I~π=1~+、激发能为146．9 kev的同质异能态构成了一对GM伙伴态；8．在过去的放射性衰变测量中，提供了三个2~+激发态(激发能分别为117．7 kev、74．95 kev和316 kev)。其中两个2~+态(117．7和74．95 kev)同时指定具有{πh_(11／2)[523↑]7／2~-direct X vh_(9／2)[521↓]3／2~-}K~π=2~+组态。这里，我们指定1 17．7 kev的2~+激发态为{πg_(7／2)[404↓]7／2~+ direct X vi_(l3／2)[651↓]3／2~+}K~π=2+组态，即与本实验建立的亚晕带内禀激发态构成了一对GM伙伴态，而74．95 kev的2~+激发态指定为 {πh_(11/2)[523↑]7／2~-direct X vh_(9/2)[521↓]3／2~-}K~π=2~+组态，即与基态构成了一对GM伙伴态。基于本实验中K~π=9~+激发态的观测及其转动带的建立，我们指定激发能为3 1 6 kev的2~+激发态具有{πh_(11/2)[523↓]7／2~-direct X vh_(11/2)[505个]1 1／2~-}K~π=2~+组态，即这两个态构成了一对GM伙伴态；9．通过本实验、提供了~(158)Ho中各能态的跃迁强度和跃迁几率等数据。概括起来，奇奇核~(158)Ho的能级纲图大大完善了。综合本实验观测到的高自旋转动带结构和放射性测量中的部分激发态信息，我们可以整理出10对GM伙伴态，并提供了四个分别对应自旋平行和反平行耦合的GM能量漂移(GM Shift)，即：{πh_(ll／2)[523]7／2~-direct Xvh_(9／2)[521]3／2~-}K~π=5~+、2~+，EGM=101．4 kev；{πh_(11/2)[523] 7／2~-direct X vd_(3／2)[402]3／2~+}K~π=5~-、2~-，E_(GM)=64．1 kev；{πd_(5/2)[402]5／2~+direct X vh_(9／2)[521]3／2~-}K~π =4~-、1~-，E_(GM)=113．3 kev；{πh_(11/2)[523]7／2~-direct Xvf_(7/2)[523]5／2~-}K~π=6~+、1~+，EGM=255．7 keV。(二)奇奇核~(124)Cs高自旋态的实验研究在原子能院的HI-13串列加速器上，利用~（116）Sn（~（11)B，3nγ)~(124)Cs融合蒸发反应(束流轰击能E_(lab.)=45 MeV)，对奇奇核~(124)Cs的高自旋态进行了布居。探测阵列由10个高纯锗探测器和一个小平面探测器组成。数据反演后，总的两重符合事件数达到160x10~6。实验结果概括如下：1．高自旋转动带的信息更丰富了：建立了三个新的转动带结构，其中两个耦合带、一个退耦带，组态分别为：{πh_(11／2)[550]1／2~- direct X vhd_(5/2)[413]5／2~+}K~π=3~-、{πg_(7／2)[413]5／2~+direct X vg_(7/2)[402】5／2~+}K~π=5~+以及{πh_(11/2)[550]1／2~- direct X vd_(3/2)[400]l／2~+}K~π=1~-；2．低激发态的信息更丰富了：观测到了20多条新的低激发态跃迁，增加了10多个新的低激发态；3．转动带之间以及转动带与低激发态间耦合的信息大大丰富了：在过去的研究中观测到了三个彼此孤立、悬空的转动带结构，这里指定它们的组态为：{πh_(11／2) [550]1／2~-direct X vh_(11/2)[523]7／2~-}K~π=4~+(晕 带) ； {πh_(11/2)[550]1／2~- (direct X)vg_(7/2)[402]5/2~+}K~π=3~-(亚晕带：布居强度仅次于晕带)；{πh_(11/2)[550]1/2~-(direct X)vs_(1/2)[411]1／2~+}K~π=1~-(双退耦结构)。其中，亚晕带(yrare band)通过至少三个独立的退激路径与低激发态联系起来；同时，建立了晕带与亚晕带间的多条连接关系。其它转动带分别与晕带和亚晕带联系起来，从而，在奇奇核~(124)Cs中，转动带的"悬空"不再存在，限定了各转动带中能级的激发能位援，并通过这些连接跃迁多极性的分析，分别指定了各能态的自旋和宇称。4．基于本实验建立的连接关系，晕带的最低态(124kev射线贯入能级)的激发能为618．9kev，该能量值比过去研究中的同一能级高出11．7kev。这表明原能级纲图中晕带的退激途径漏掉了一个11．7kev的"能隙"(根据Weisskopf估计，该能隙很可能由两个偶极跃迁构成)。该"能隙"的漏观测，正是导致过去实验中无法正确指定晕带自旋的原因所在；

中能重离子碰撞中激发热核性质同位旋效应的实验研究

中能重离子碰撞中的核反应机制及其形成的高激发热核的性质是中能重离子物理研究的重要领域，而高激发热核性质的同位旋效应研究是这一领域的热点之一。选取了具有不同N亿比的反应体系以研究激发热核性质的同位旋效应。本论文涉及的反应系统三对共六个反应体系：55MeV／u~(40)Ar+~(58.64)Ni、30MeV/u~(40)Ar+~(112,124)Sn、35Mev／u~(36)Ar+~(112,124)Sn，这六个反应体系的N／z比分别为1.13，1.26、1.24，1.41、1.18，1.35。分别从带电粒子多重性、相对态布居核温度、关联函数等角度研究了这三对反应体系高激发热核性质的同位旋效应。在55MeV／u 40Ar+58,64Ni核反应中，用兰州4π带电粒子探测器阵列测量带电粒子多重性，研究了He和中等质量碎片的产额与反应系统的同位旋的关系，以及这种同位旋效应与反应系统的碰撞参数（即碰撞的激烈程度）、系统的激发能的变化关系。对两个反应系统，观察到带电粒子多重性中He的比分随带电粒子多重性的增加而增大，带电粒子多重性中IMF的比分随带电粒子多重性的增加而先增大，后减小的规律。两个反应系统虽然具有相同的核电荷数，但轻粒子He和中等质量碎片在多重性中的比分有明显的同位旋相关性。在30Mev／u40Sn、35MeV/u~(40)Ar~(112，124)Sn、35Mev／u 36Ar＋112,124Sn反应中用13单元望远镜探测器阵列测量了小角关联粒子。由价a关联函数提取了30Mev／u 40Ar＋112，12Sn反应系统中激发热核的态布居核温。对于不同同位旋反应系统舜UAr＋112Sn和4VAr+124Sn，提取的相对杰布居核温度分别是4.18+0.28/0.21MEV和4.10士0.22/0.20MeV；考察态布居核温度和粒子能量的关薰时，观察到两个系统的发射温度均随着粒子能量的增加而降低，缺中子系统40Ar＋l12Sn中由低能时的5.13士.30/0.26MEV降低到高能时的3.87士0.37/0.29MeV，丰中子系统40Ar＋124Sn中由低能时的5．39士0.30/0.26MeV降低到高能时的3．32士MeV。讨论了这种布居态核温度的同位旋相关性。在35Mev／u 36Ar＋112，124Sn反应中提取了洲F（3‘25）的约化速度关联函数。相对丰中子36Ar＋124Sn系统的IMF关联函数在小约化速度处反关联程度更强，表明36Ai＋124Sn系统的发射IMF的平均时间更短。用MENEKA程序提取了两个系统IMF的平均发射时间，36Ai＋112sn反应中IMF的发射时间约为150fm/c，而36Ar十124Sn反应IME的发射时间稍短，约为120fm／c。以关联IMF的单核子总能量／动量为窗条件，发现低能IMF关联函数几乎没有差别，而高能IMF关联函数在小约化速度处的差别更为明显，表明两个系统IMF关联函数的同位旋效应可能来自于IMF的早期发射。为了得到进一步的信息，我们提取了高动量窗条件下的IMF发射时间，它们比平均发射时间短，36Ar＋112Sn反应中高能IMF的发射时间约为100蒯c，而36Ai＋124Sn反应中IMF的发射时间则更短，约为50fm/c。

Performance comparison of low-temperature direct alcohol fuel cells with different anode catalysts

Low-temperature polymer electrolyte membrane fuel cells directly fed by methanol and ethanol were investigated employing carbon supported Pt, PtSn and PtRu as anode catalysts, respectively. Employing Pt/C as anode catalyst, both direct methanol fuel cell (DMFC) and direct ethanol fuel cell (DEFC) showed poor performances even in presence of high Pt loading on anode. It was found that the addition of Ru or Sn to the Pt dramatically enhances the electro-oxidation of both methanol and ethanol. It was also found that the single cell adopting PtRu/C as anode shows better DMFC performance, while PtSn/C catalyst shows better DEFC performance. The single fuel cell using PtSn/C as anode catalyst at 90degreesC shows similar power densities whenever fueled by methanol or ethanol. The cyclic voltammetry (CV) and single fuel cell tests indicated that PtRu is more suitable for DMFC while PtSn is more suitable for DEFC. (C) 2003 Elsevier B.V. All rights reserved.

Effects of treatment in different atmosphere on Pt3Sn/C electrocatalysts for ethanol electro-oxidation

Pt3Sn/C catalyst was prepared by a modified polyol process and treated in air, H-2/Ar, and Ar atmosphere, respectively. XRD analyses indicate that all of these catalysts have face-centered cubic (fcc) crystal structure. Temperature-programmed reduction (TPR) experiments show that more Sn exists in zero-valence in the Ar-treated PtSn catalyst than in the others. Cyclic voltammetry (CV), chronoamperometry (CA) experiments, and the performance tests of direct ethanol fuel cell (DEFC) indicate that the catalytic activity of PtSn/C for ethanol oxidation was affected significantly by the chemical state of Sn in catalyst particles. The as-prepared PtSn/C gives the higher power density, while Ar-treated PtSn/C shows the lower cell performance. It seems that the multivalence Sn rather than the zero-valence Sn in the PtSn catalyst is the favorable form for ethanol oxidation. Energy dispersion X-ray analysis (EDX) of the PtSn/C-as prepared and PtSn/C (after stability test) shows the active species (platinum, tin, and oxygen) composition changed to a different extent. Further attempt to improve the catalyst stability is needed.

Preparation and characterization of PtSn/C anode electrocatalysts for direct ethanol fuel cell

Highly active PtSn/C catalyst was prepared by a polyol method. The catalyst was reduced in H-2/Ar atmosphere at 600 degreesC for 2 h in order to obtain different metallic phase. TEM images show uniform dispersion of spherical metal nanoparticles with average diameters of 1.8 and 3.9 nm for the as-prepared and treated catalysts, respectively. UV-vis spectrophotometry is employed to monitor the preparation process and the results indicate that Pt-Sn complex formed once the precursors of Pt and Sn were mixed together. The structure properties of the samples were characterized using X-ray diffraction. The results show that after reduction, the catalyst tends to form PtSn alloy. TPR experiment results show that Sn exists in multivalent state in the as-prepared sample while only zero-valence Sn was detected in the treated sample, while it could not be excluded that the multivalent tin existed in the treated sample. Cyclic voltammetry (CV) technique and single direct ethanol fuel cell (DEFC) tests indicate that the as-prepared catalyst possesses superior catalytic activity for ethanol oxidation to the treated sample. The results suggest that Pt and multivalent Sn are the active species for ethanol oxidation. (C) 2004 Elsevier B.V. All rights reserved.

Pt-based anode catalysts for direct ethanol fuel cells

In the present work, several carbon supported PtSn and PtSnRu catalysts were prepared with different atomic ratios and tested in direct ethanol fuel cells (DEFC) operated at lower temperature (T=90 degreesC). XRD and TEM results indicate that all of these catalysts consist of uniform nano-sized particles of narrow distribution and the average particle sizes are always less than 3.0 nm. As the content of Sn increases, the Pt lattice parameter becomes longer. Single direct ethanol fuel cell tests were used to evaluate the performance of carbon supported PtSn catalysts for ethanol electro-oxidation. It was found that the addition of Sn can enhance the activity towards ethanol electro-oxidation. It is also found that a single DEFC of Pt/Sn atomic ratioless than or equal to2, "Pt1Sn1/C, Pt3Sn2/C, and Pt2Sn1/C" shows better performance than those with Pt3Sn1/C and Pt4Sn1/C. But even adopting the least active PtSn catalyst, Pt4Sn1/C, the DEFC also exhibits higher performance than that with the commercial Pt1Ru1/C, which is dominatingly used in PEMFC at present as anode catalyst for both methanol electro-oxidation and CO-tolerance. At 90 degreesC, the DEFC exhibits the best performance when Pt2Sn1/C is adopted as anode catalysts. This distinct difference in DEFC performance between the catalysts examined here is attributed to the so-called bifunctional mechanism and to the electronic interaction between Pt and Sn. It is thought that -OHads, Surface Pt active sites and the ohmic effect of PtSn/C catalyst determines the electro-oxidation activity of PtSn catalysts with different Pt/Sn ratios. (C) 2004 Elsevier B.V. All rights reserved.

Pt based anode catalysts for direct ethanol fuel cells

In the present work several Pt-based anode catalysts supported on carbon XC-72R were prepared with a novel method and characterized by means of XRD, TEM and XPS analysis. It was found that all these catalysts are consisted of uniform nanosized particles with sharp distribution and Pt lattice parameter decreases with the addition of Ru or Pd and increases with the addition of Sn or W. Cyclic voltammetry (CV) measurements and single direct ethanol fuel cell (DEFC) tests jointly showed that the presence of Sn, Ru and W enhances the activity of Pt towards ethanol electro-oxidation in the following order: Pt1Sn1/C > Pt1Ru1/C > Pt1W1/C > Pt1Pd1/C > Pt/C. Moreover, Pt1Ru1/C further modified by W and Mo showed improved ethanol electro-oxidation activity, but its DEFC performance was found to be inferior to that measured for Pt1Sn1/C. Under this respect, several PtSn/C catalysts with different Pt/Sn atomic ratio were also identically prepared and characterized and their direct ethanol fuel cell performances were evaluated. It was found that the single direct ethanol fuel cell having Pt1Sn1/C or Pt3Sn2/C or Pt2Sn1/C as anode catalyst showed better performances than those with Pt3Sn1/C or Pt4Sn1/C. It was also found that the latter two cells exhibited higher performances than the single cell using Pt1Ru1/C, which is exclusively used in PEMFC as anode catalyst for both methanol electro-oxidation and CO-tolerance. This distinct difference in DEFC performance between the catalysts examined here would be attributed to the so-called bifunctional mechanism and to the electronic interaction between Pt and additives. It is thought that an amount of -OHads, an amount of surface Pt active sites and the conductivity effect of PtSn/C catalysts would determine the activity of PtSn/C with different Pt/Sn ratios. At lower temperature values or at low current density regions where the electro-oxidation of ethanol is considered not so fast and its chemisorption is not the rate-determining step, the Pt3Sn2/C seems to be more suitable for the direct ethanol fuel cell. At 75 degreesC, the single ethanol fuel cell with Pt3Sn2/C as anode catalyst showed a comparable performance to that with Pt2Sn1/C, but at higher temperature of 90 degreesC, the latter presented much better performance. It is thought from a practical point of view that Pt2Sn1/C, supplying sufficient -OHads and having adequate active Pt sites and acceptable ohmic effect, could be the appropriate anode catalyst for DEFC. (C) 2003 Elsevier B.V. All rights reserved.