大洋多金属结核和深海沉积物标准物质中铂族元素的中子活化分析

采用镍锍试金预富集中子活化分析方法，测定了大洋多金属结核标准物质ＧＳＰＮ２、ＧＳＰＮ３和深海沉积物标准物质ＧＳＭＳ２、ＧＳＭＳ３中的铂族元素；根据大洋样品成分特征，对常规的镍锍试金配方和熔炼条件作了改善；计算了活化分析中的铂族元素干扰核反应，校正了Ａｕ对Ｐｔ的二级干扰；选用羰基化镍粉配料，降低了铂族元素空白值。用国家一级标准物质ＧＢＷ０７１０２作了对照分析，结果与标准值相符。

太平洋多金属结核中的锰矿物及其相变

从太平洋多金属结核中鉴定出的锰矿物有水羟锰矿、钙锰矿、水钠锰矿、布塞尔矿、布塞尔矿－锰钴土混层矿物及纤锌锰矿。锰矿物的分布特点是，太平洋中部ＣＰ区以水羟锰矿为主，钙锰矿次之；ＣＣ区以片状钙锰矿为主，水羟锰矿次之；东太平洋海盆以片状钙锰矿和布塞尔矿为主，水羟锰矿较少。通过锰矿物相变实验，探讨了水羟锰矿－钙锰矿、水钠锰矿－布塞尔矿、钙锰矿－布塞尔矿。

多金属结核锶铅同位素地球化学特征的初步研究

研究东太平洋海盆多金属结核锶铅同位素地球化学特征。结果表明,结核中锶同位素与铅同位素不相关,锶同位素可用于划分和对比结核生长时代,而铅同位素能指示物源的性质。锶同位素记录表明,有些结核生长历史较短,生长较快,生长过程中不翻转亦不会被“沉积物雨”所淹埋,而铅同位素记录表明结核明显受到了上幔源物质输入的影响。

熔炼浸出法处理大洋多金属结核研究现状及发展

阐明了熔炼浸出法的基本原理和主要过程，概括了该方法的研究现状。并以试验为基础，论证了熔炼浸出的发展，即熔炼—锈蚀—萃取新工艺的可行性。

太平洋CC区多金属结核的分类问题

本文论述了多金属结核分类的目的及应遵循的原则，结合DY85－4航次对结核的调查研究，依据结核的表面构造特征将结核分为：光滑型、粗糙型及光滑十粗糙型。详细地叙述了不同类型多金属结核的特征及形成环境。通过对前人关于多金属结核分类的回顾和评述，指出了前人分类的某些缺点和不足，并着重强调了我们采用分类的优点和可行性。

Lix622从大洋多金属结核盐酸浸出液除铁余液中萃取铜的研究

本文研究了用Lix622作萃取剂,CuSO_4溶液作反萃剂从大洋多金属结核盐酸浸出液中萃取铜的工艺,考察了pH值、Lix622浓度、相比、时间对萃取及H_2SO_4浓度、Cu^(2+)浓度、相比、时间对反萃的影响,并进行了模拟实验.

深海多金属结核开采技术纵览

为了获得商业性开发深海矿产资源所必须的技术手段,近年来一些发达国家对深海多金属开采设备作了捷足先登的开发性研究。本文仅就目前出现的集矿系统中各类设备的结构、原理、工作方式及特点作了概括报导。文中还介绍了四种扬矿方法,其中连续索斗法的采集面因缆绳的缠绕而受到局限;气力和水力提升法是目前各国优先选取的方法;穿梭潜孔法是一种很有前途的方法。

Preparation and electrochemical lithium storage performance of porous silicon microsphere composite with metal modification and carbon coating

This work adopts a multi⁃step etching⁃heat treatment strategy to prepare porous silicon microsphere com⁃posite with Sb⁃Sn surface modification and carbon coating(pSi/Sb⁃Sn@C),using industrial grade SiAl alloy micro⁃spheres as a precursor.pSi/Sb⁃Sn@C had a 3D structure with bimetallic(Sb⁃Sn)modified porous silicon micro⁃spheres(pSi/Sb⁃Sn)as the core and carbon coating as the shell.Carbon shells can improve the electronic conductivi⁃ty and mechanical stability of porous silicon microspheres,which is beneficial for obtaining a stable solid electrolyte interface(SEI)film.The 3D porous core promotes the diffusion of lithium ions,increases the intercalation/delithia⁃tion active sites,and buffers the volume expansion during the intercalation process.The introduction of active met⁃als(Sb⁃Sn)can improve the conductivity of the composite and contribute to a certain amount of lithium storage ca⁃pacity.Due to its unique composition and microstructure,pSi/Sb⁃Sn@C showed a reversible capacity of 1247.4 mAh·g^(-1) after 300 charge/discharge cycles at a current density of 1.0 A·g^(-1),demonstrating excellent rate lithium storage performance and enhanced electrochemical cycling stability.

Synthesis and structures of cdq‑topological quaternary and(4,4,8)‑c topological quinary Zn‑MOFs with both oxalic acid and triazole ligands

Different solvothermal reactions of ZnC2O_(4)with oxalic acid(H_(2)ox)and 1,2,4-triazole(Htrz)successfully gave a new quaternary(NJTU-Bai83,NJTU-Bai=Nanjing Tech University Bai's group)and a new quinary(NJTU-Bai84)anionic metal-organic frameworks(MOFs),where NJTU-Bai83=(Me_(2)NH_(2))2[Zn_(3)(trz)_(2)(ox)_(3)]·2H_(2)O and NJTU-Bai84=(Me_(2)NH_(2))[Zn_(3)(trz)_(3)(ox)_(2)]·H_(2)O,respectively.With the[Zn_(2)(ox)4(trz)_(2)]secondary building unit(SBU)in NJTU-Bai83 replaced by the[Zn_(3)(ox)_(2)(trz)_(6)]and planar[Zn(ox)_(2)(trz)_(2)]ones in NJTU-Bai84,2D supramolecular building layers(SBLs)are changed from the A-layer and B-layer to another A-layer,while pillars are transformed from the tetrahedral[Zn(ox)_(2)(trz)_(2)]SBU to the irregular tetrahedral[Zn(ox)_(2)(trz)_(2)]and planar[Zn(ox)_(2)(trz)_(2)]SBUs.Thus,cdq-topological quaternary NJTU-Bai83 is tuned to(4,4,8)-c new topological quinary NJTU-Bai84.Two MOFs were well characterized by powder X-ray diffraction,thermogravimetric analysis,elemental analysis,etc.CCDC:2351819,NJTU-Bai83;2351820,NJTU-Bai84.

深海锰结核中螺旋状超微生物化石的发现及其意义

对东太平洋深海瘤状锰结核透射电镜的系统观察和分析表明，瘤状锰结核的包壳，即奇异叠层石的建造者是纳米级的螺旋状微生物。螺旋状微生物体的菌落呈圆盘状至不规则分技状，菌落中心下陷。营养菌丝体呈辐射状从中央向周围生长。营养菌丝体的柬宽度为１７～６０ｎｍ，呈双分叉。生殖菌丝体由粗细不等的螺旋状丝体组成。螺旋状丝体的宽度为３～２５ｎｍ，长度为３６～２００ｎｍ，螺环宽度（菌丝直径）为２～４ｎｍ。螺旋状生殖丝体分叉，抱囊呈球形，深陷于螺旋状生殖菌丝体之中。抱囊直径为９～５０ｎｍ、抱囊内赋存有球形抱子，球形抱子直径为４～６ｎｍ。本文将该纳米级螺旋状微生物化石暂归入放线菌纲，建立一个新属种，即太平洋螺球抱菌（Ｓｐｉｒｉｓｏｓｐｈａｅｒｏｓｐｏｒａｐａｃｉｆｉｃａ）。毫无疑问，纳米级微生物化石的发现对深海锰结核以及生命起源的研究将起一定的促进作用，对生物矿物学、生物地球化学、生物成矿理论、微生物学都具有重要的意义。

中国深海采矿

随着国民经济建设的发展,中国工业对铜、镍、钴、锰四种金属的需求量也逐步增长。目前这些金属在中国尚供不应求。因此,开发深海多金属结核对中国经济建设具有重要意义。本文介绍中国深海采矿的前期研究工作,目前中国对开发深海多金属结核所具备的条件和中国大洋矿产资源研究开发协会概况。最后,作者以个人观点叙述了中国海洋采矿企业为下世纪初在申请的国际海底矿区实现工业开采目标而可能实施的深海采矿研究计划和技术路线。

Effect of melt superheat on structural uniformity of lotus-type porous metals prepared by unidirectional solidification

Structural uniformity is an important parameter influencing physical and mechanical properties of lotus-type porous metals prepared by directional solidification of metal-gas eutectic (Gasar). The effect of superheat on structural uniformity as well as average porosity, pore morphology of porous metals was studied. The experimental results show that, when the superheat is higher than a critical value (ΔTc), the bubbling or boiling phenomenon will occur and the gas bubbles will form in the melt and float out of the melt. As a result, the final porosity will decrease. In addition, a higher superheat will simultaneously cause a non-uniform porous structure due to the pores coalescence and bubbling phenomenon. Finally, a theoretical model was developed to predict the critical superheat for the hydrogen to escape from the melt and the corresponding escapement ratio of hydrogen content. Considering the escapement of hydrogen, the predicted porosities are in good agreement with the experimental results.

Syntheses of Two Chiral Clusters [η~5-C_5H_4C(NR)CH_3]- RuNiM(CO)_5(μ_3-S) (R =NH-C_6H_3-2,4-(NO_2)_2,M=Mo,3;M=W,4) and the Single-crystal Structure of Cluster 3

The new chiral clusters [h5-C5H4C(NR)CH3]RuNiM(CO)5(m3-S) (R = NH-C6H3-2,4- (NO2)2, M = Mo, 3; M = W, 4) were synthesized and the structure of cluster 3 was determined by single-crystal X-ray analysis. Crystal data: C23H16O9N4MoNiRuS, Mr = 780.18, orthorhombic, space group Pbca with the following crystallographic parameters: a = 13.207(4), b = 16.036(5), c = 25.513(8) , Z = 8, V = 5403(3) 3, Dc = 1.918 g/cm3, m = 1.834 mm-1 and F(000) = 3072. The final R = 0.0512 and wR = 0.1132 for 2525 reflections with I > 2.00s(I).

Static and dynamic design based on hierarchical optimization for materials and structure of porous metals

A static and dynamic collaborative optimization method for materials and structure with uniform periodic microstructure is presented.The sensitivity formulae of hierarchical optimization,i.e.,material design,structure design and integrated design for porous metals,are given.On the base of the hierarchical optimization model,numerical experiments of an MBB beam and a cantilever one were carried out.Based on porous metals bearing multi-functionality,the differences and applicability of hierarchical optimization are discussed in the structure loading field.It is concluded that structure design is mainly oriented to structure efficiency,material design is mainly oriented to multi-functionality,and integrated design is oriented to structure efficiency and multi-functionality.This work provides some useful ideas for the selection of porous metals design method.

Synthesis,structure and photoluminescence of two porous metal-organoboron frameworks with rtl topology

Rigid trigonal tris(3-pyridylduryl)borane L was synthesized through four steps in good overall yield from readily available 1,2,4,5-tetramethylbenzene and was used to construct two porous cadmium(II) complexes Cd(L)X2.G(X = Cl,Br;G = guset molecules),1(Cd(L)Cl2.EtOH.iPrOH.3H2O) and 2(Cd(L)Br2.MeOH.C7H8.3H2O),under mild reaction conditions.1 and 2 are isostructural and featured with 3D porous metal-organoboron framewoks with rtl topology,in which L acts as a 3-connected node while a dicadmium motif serves as 6-connected node.In addition,1 and 2 exhibit strong photoluminescence in the visible region and 1 shows moderate adsorption ability of carbon dioxide at 273 K.

Li_(x)Cu alloy nanowires nested in Ni foam for highly stable Li metal composite anode

Porous metal architectures are widely adopted as three-dimensional conducting scaffolds for constructing Li metal composite anodes,whereas their macropores hinder their practical application due to limited surface area and large pore size of few hundred micrometers.In this work,a network of Li_(x)Cu solid solution alloy nanowires is in situ formed via infiltrating molten Li-Cu alloy into Ni foam and subsequent cooling treatment,whereby a three-component composite anode consisting of Li metal,Li_(x)Cu alloy,and Ni foam is fabricated.The Li_(x)Cu nanowires nested as secondary frame split the macropores into micropores,enlarging the active surface area and inducing uniform Li deposition significantly.The lithiophilicity of the alloy wires and the shrunken void size built by the hierarchical architecture can further tune the nucleation and growth behavior of Li.The multiscale synergetic effect between the primary and secondary scaffold guarantees the composite anode sheet with extraordinarily long-term cycling stability even under high current rates.

Dynamic metal patterns of wrinkles based on photosensitive layers

Regulating metal surfaces with micro-/nanoscale structures is of great significance for both material science and potential applications.However,the intrinsic properties of metals,such as fixed isotropic moduli and inflexible structures,in a sense present major limitations in developing next-generation smart patterned surfaces.In this work,a facile and general patterning strategy is proposed to endow insensitive metal surfaces with controllable spontaneous topologies and dynamic performance by exquisitely introducing an essential photosensitive interlayer.The arresting anthracene-containing photocrosslinking interlayer can selectively predetermine the anisotropic property of compliant bilayers without damaging metals’homogeneous properties,and realize a changeable stiff/soft layer.Furthermore,the mechanical transition mechanism of the self-adaptive wrinkling modes in metalbased trilayer systems is revealed to pave the pathway for regulating functional wrinkled metal surfaces.This photodriven metal patterning strategy can promote the development of brand-new methods for tuning the instability of multilayered materials,and be potentially applied in smart optical devices with dynamic reflectance,including light gratings and"magic"mirrors.

Recent development of efficient electrocatalysts derived from porous organic polymers for oxygen reduction reaction

Porous organic polymers(POPs) have recently emerged as promising candidates for catalyzing oxygen reduction reaction(ORR).Compared to conventional Pt-based ORR catalysts, these newly developed porous materials, including both non-precious metal based catalysts and metal-free catalysts, are more sustainable and cost-effective. Their porous structures and large surface areas facilitate mass and electron transport and boost the ORR kinetics. This mini-review will give a brief summary of recent development of POPs as electrocatalysts for the ORR. Some design principles, different POP structures, key factors for their ORR catalytic performance, and outlook of POP materials will be discussed.

Bimetal-organic framework-derived carbon nanocubes with 3D hierarchical pores as highly efficient oxygen reduction reaction electrocatalysts for microbial fuel cells

Noble metal-free and highly efficient electrocatalytic materials with hierarchically porous structures continue to be studied for the oxygen reduction reaction(ORR) in microbial fuel cells(MFCs). We report bimetal-organic framework(bi-MOF)-derived nanocubic Swiss cheese-like carbons with a novel three-dimensional hierarchically porous structure(3D Co-N-C) prepared by utilizing cetyltrimethylammonium bromide(CTAB) as a structure-directing agent to control the formation of a nanocubic skeleton, and silica spheres as a template to form a mesoporous structure. The elemental composition and chemical morphology of this material can be tuned through the Zn/Co ratio to optimize its ORR catalytic activity. The optimized 3D Co-N-C displays excellent ORR catalytic performance(half-wave potential as high as 0.754 V vs. reversible hydrogen electrode and diffusion-limiting current density of 5.576 mA cm^(-2)) in 0.01 mol L^(-1) phosphate-buffered saline(PBS electrolyte),showing it can compete with the commercial 20 wt% Pt/C catalysts. The catalytic capability and long-term durability of 3D Co-N-C as an air-filled cathode electrocatalyst in an MFC device are tested, showing that the 3D CoNC-MFC can reach a high power density of 1257 mW m^(-2) and provide a competitive voltage during a periodic feeding operation for 192 h;these values are much higher than those of the Pt/C-MFC.