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化学专业外文文献原稿和译文

化学专业外文文献原稿和译文
化学专业外文文献原稿和译文

外文文献原稿和译文

原稿

Facile synthesis of hierarchical core–shell Fe3O4@MgAl–LDH@Au as magnetically recyclable catalysts for catalytic oxidation of alcohols

A novel core–shell structural Fe3O4@MgAl–LDH@Au nanocatalyst was simply synthesized via supporting Au nanoparticles on the MgAl–LDH surface of Fe3O4@MgAl–LDH nanospheres. The catalyst exhibited excellent activity for the oxidation of 1-phenylethanol, and can be effectively recovered by using an external magnetic field.

The selective oxidation of alcohols to the corresponding carbonyl compounds is a greatly important transformation in synthesis chemistry. Recently, it has been disclosed that hydrotalcite (layered double hydroxides: LDH)-supported Cu, Ag and Au nanoparticles as environmentally benign catalysts could catalyse the oxidation of alcohol with good efficiency. In particular, the Au nanoparticles supported on hydrotalcite exhibit high activity for the oxidation of alcohols under atmospheric O2 without additives. It has been extensively demonstrated that the activity of the nanometre-sized catalysts will benefit from decreasing the particle size. However, as the size of the support is decreased, separation using physical methods, such as filtration or centrifugation, becomes a difficult and time-consuming procedure. A possible solution could be the development of catalysts with magnetic properties, allowing easy separation of the catalyst by simply applying an external magnetic field. From the green chemistry point of view, development of highly active, selective and recyclable catalysts has become critical. Therefore, magnetically separable nanocatalysts have received increasing attention in recent years because the minimization in the consumption of auxiliary substances, energy and time used in achieving separations can

result in significant economical and environmental benefits.

Magnetic composites with a core–shell structure allow the integration of multiple functionalities into a single nanoparticle system, and offer unique advantages for applications, particularly in biomedicine and catalysis. However it is somewhat of a challenge to directly immobilize hierarchical units onto the magnetic cores. In our previous work, the Fe3O4 submicro-spheres were first coated with a thin carbon layer, then coated with MgAl–LDH to obtain an anticancer agent-containing Fe3O4@DFUR–LDH as drug targeting delivery vector. Li et al. prepared Fe3O4@MgAl–LDH through a layer-by-layer assembly of delaminated LDH nanosheets as a magnetic matrix for loading W7O24as a catalyst. These core–shell structural nanocomposites possess the magnetization of magnetic materials and multiple functionalities of the LDH materials. Nevertheless, these reported synthesis routes need multi-step and sophisticated procedures. Herein, we design a facile synthesis strategy for the fabrication of a novel Fe3O4@MgAl–LDH@Au nanocatalyst, consisting of Au particles supported on oriented grown MgAl–LDH crystals over the Fe3O4 nanospheres, which combines the excellent catalytic properties of Au nanoparticles with the superparamagnetism of the magnetite nanoparticles. To the best of our knowledge, this is the first instance of direct immobilization of vertically oriented MgAl–LDH platelet-like nanocrystals onto the Fe3O4 core particles by a simple coprecipitation method and the fabrication of hierarchical magnetic metal-supported nanocatalysts via further supporting metal nanoparticles.

As illustrated in Scheme 1, the synthesis strategy of Fe3O4@MgAl–LDH@Au involves two key aspects. Nearly monodispersed magnetite particles were pre-synthesized using a surfactant-free solvothermal method. First, the Fe3O4 suspension was adjusted to a pH of ca. 10, and thus the obtained fully negatively charged Fe3O4spheres were easily coated with a layer of oriented grown carbonate–MgAl–LDH via electrostatic attraction followed by interface nucleation and crystal growth under dropwise addition of salts and alkaline solutions. Second, Au nanoparticles were effectively supported on thus-formed support Fe3O4@MgAl–LDH by a deposition–precipitation method (see details in ESI).

Fig. 1 depicts the SEM/TEM images of the samples at various stages of the fabrication of the Fe3O4@MgAl–LDH@Au nanocatalyst. The Fe3O4nanospheres (Fig. 1a) show a

smooth surface and a mean diameter of 450 nm with a narrow size distribution (Fig. S1, ESI). After direct coating with carbonate–MgAl–LDH (Fig. 1b), a honeycomb like morphology with many voids in the size range of 100–200 nm is clearly observed, and the LDH shell is composed of interlaced platelets of ca. 20 nm thickness. Interestingly, the MgAl–LDH shell presents a marked preferred orientation with the c-axis parallel to, and the ab-face perpendicular to the surface of the magnetite cores, quite different from those of a previous report. A similar phenomenon has only been observed for the reported LDH films and the growth of layered hydroxides on cation-exchanged polymer resin beads. The TEM image of two separate nanospheres (Fig. 1d) undoubtedly confirms the core–shell structure of the Fe3O4@MgAl–LDH with the Fe3O4 cores well-coated by a layer of LDH nanocrystals. In detail, the MgAl–LDH crystal monolayers are formed as large thin nanosheet-like particles, showing a edge-curving lamella with a thickness of ca. 20 nm and a width of ca. 100 nm, growing from the magnetite core to the outer surface and perpendicular to the Fe3O4surface. The outer honeycomb like microstructure of the obtained core–shell Fe3O4@MgAl–LDH nanospheres with a surface area of 43.3 m2g_1 provides abundant accessible edge and junction sites of LDH crystals making it possible for this novel hierarchical composite to support metal nanoparticles. With such a structural morphology, interlaced perpendicularly oriented MgAl–LDH nanocrystals can facilitate the immobilization of nano-metal particles along with avoiding the possible aggregation.

Scheme 1 The synthetic strategy of an Fe3O4@MgAl–LDH@Au catalyst.

Fe3O4 (a), Fe3O4@MgAl–LDH (b and d) and Fe3O4@MgAl–LDH@Au (c, e, f and g).

Fig. 2 XRD patterns of Fe3O4 (a), Fe3O4@MgAl–LDH (b) and Fe3O4@MgAl–LDH@Au

(c).

The XRD results (Fig. 2) demonstrate that the Fe3O4@MgAl–LDH nanospheres are

composed of an hcp MgAl–LDH (JCPDS 89-5434) and fcc Fe3O4 (JCPDS 19-0629). It can

be clearly seen from Fig. 2b that the series (00l) reflections at low 2θ angles are

significantly reduced compared with those of single MgAl–LDH (Fig. S2, ESI), while the (110) peak at high 2θangle is clearly distinguished with relatively less decrease, as revealed by greatly reduced I(003)/I(110) = 0.8 of Fe3O4@MgAl–LDH than that of MgAl–LDH (3.9). This phenomenon is a good evidence for an extremely well-oriented assembly of MgAl–LDH platelet-like crystals consistent with the c-axis of the crystals being parallel to the surface of an Fe3O4core. The particle dimension in the c-axis is calculated as ~ 25 nm using the Scherrer equation (eqn S1, ESI) based on the (003) line width (Fig. 2b), in good agreement with the SEM/TEM results. The energy-dispersive X-ray (EDX) result (Fig. S3, ESI) of Fe3O4@MgAl–LDH reveals the existence of Mg, Al, Fe and O elements, and the Mg/Al molar ratio of 2.7 close to the expected one (3.0), indicating the complete coprecipitation of metal cations for MgAl–LDH coating on the surface of Fe3O4.

The FTIR data (Fig. S4, ESI) further evidence the chemical compositions and structural characteristics of the composites. The as-prepared Fe3O4@MgAl–LDH nanosphere shows a sharp absorption at ca. 1365 cm_1 being attributed to the ν3 (asymmetric stretching) mode of CO32_ ions and a peak at 584 cm_1 to the Fe–O lattice mode of the magnetite phase, indicating the formation of a CO32–LDH shell on the surface of the Fe3O4 core. Meanwhile, a strong broad band around 3420 cm_1 can be identified as the hydroxyl stretching mode, arising from metal hydroxyl groups and hydrogen-bonded interlayer water molecules. Another absorption resulting from the hydroxyl deformation mode of water, δ(H2O), is recorded at ca. 1630 cm_1.

Based on the successful synthesis of honeycomb like core–shell nanospheres, Fe3O4@MgAl–LDH, our recent work further reveals that this facile synthesis approach can be extended to prepare various core–shell structured LDH-based hierarchical magnetic nanocomposites according to the tenability of the LDH layer compositions, such as NiAl–LDH and CuNiAl–LDH (Fig. S3, ESI).

Gold nanoparticles were further assembled on the honeycomb likeMgAl–LDH platelet-like nanocrystals of Fe3O4@MgAl–LDH. Though the XRD pattern (Fig. 2c) fails to show the characteristics of Au nanoparticles, it can be clearly seen by the TEM of Fe3O4@MgAl–LDH@Au (Fig. 1e) that Au nanoparticles are evenly distributed on the edge

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(2) w 12… . (3) R 1,2, … (4) Δ ? ? ?others toprojectQ rcer humanresou i k 01 (5) . I t I t . (6) △ I ’s a .( ’t .) (7) (5) t I △ ,( △ ). , – a . (8) (6) (7), I ( = △* △ ). (9) =ηi / * , ηi I ; * I , * =∑=R k ki 1 δ . , . , , . 3.3 , , : = ∑∑==N i i N i Ci 11 ω i i N i i N i c t ??∑∑==1 1 ω (2) ∑∑ ==N i i N i 1 1 ω ) E i R i ki i t - ?? ∑=1 δη i c ? 2F Z 2()i t ? ) E i R i ki i t - ??∑=1 δη (3) () ,(N j i K 3,2,1,=?) (4)

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参考文献 一、翻译理论与实践相关书目 谢天振主编. 《当代国外翻译理论导读》. 天津:南开大学出版社,2008. Jeremy Munday. 《翻译学导论——理论与实践》Introducing Translation Studies---Theories and Applications. 李德凤等译. 北京:商务印书馆,2007. 包惠南、包昂. 《中国文化与汉英翻译》. 北京:外文出版社, 2004. 包惠南. 《文化语境与语言翻译》. 北京:中国对外翻译出版公司. 2001. 毕继万. 《世界文化史故事大系——英国卷》. 上海:上海外语教育出版社, 2003. 蔡基刚. 《英汉汉英段落翻译与实践》. 上海:复旦大学出版社, 2001. 蔡基刚. 《英汉写作对比研究》. 上海:复旦大学出版社, 2001. 蔡基刚. 《英语写作与抽象名词表达》. 上海:复旦大学出版社, 2003. 曹雪芹、高鄂. 《红楼梦》. 陈定安. 《英汉比较与翻译》. 北京:中国对外翻译出版公司, 1991. 陈福康. 《中国译学理论史稿》(修订本). 上海:上海外语教育出版社. 2000. 陈生保. 《英汉翻译津指》. 北京:中国对外翻译出版公司. 1998. 陈廷祐. 《英文汉译技巧》. 北京:外语教学与研究出版社. 2001. 陈望道. 《修辞学发凡》. 上海:上海教育出版社, 1979. 陈文伯. 《英汉翻译技法与练习》. 北京:世界知识出版社. 1998. 陈中绳、吴娟. 《英汉新词新义佳译》. 上海:上海翻译出版公司. 1990. 陈忠诚. 《词语翻译丛谈》. 北京:中国对外翻译出版公司, 1983. 程希岚. 《修辞学新编》. 吉林:吉林人民出版社, 1984. 程镇球. 《翻译论文集》. 北京:外语教学与研究出版社. 2002. 程镇球. 《翻译问题探索》. 北京:商务印书馆, 1980. 崔刚. 《广告英语》. 北京:北京理工大学出版社, 1993. 单其昌. 《汉英翻译技巧》. 北京:外语教学与研究出版社. 1990. 单其昌. 《汉英翻译讲评》. 北京:对外贸易教育出版社. 1989. 邓炎昌、刘润清. 《语言与文化——英汉语言文化对比》. 北京:外语教学与研究出版社, 1989. 丁树德. 《英汉汉英翻译教学综合指导》. 天津:天津大学出版社, 1996. 杜承南等,《中国当代翻译百论》. 重庆:重庆大学出版社, 1994. 《翻译通讯》编辑部. 《翻译研究论文集(1894-1948)》. 北京:外语教学与研究出版社. 1984. 《翻译通讯》编辑部. 《翻译研究论文集(1949-1983)》. 北京:外语教学与研究出版社. 1984. . 范勇主编. 《新编汉英翻译教程》. 天津:南开大学出版社. 2006. 方梦之、马秉义(编选). 《汉译英实践与技巧》. 北京:旅游教育出版社. 1996. 方梦之. 《英语汉译实践与技巧》. 天津:天津科技翻译出版公司. 1994. 方梦之主编. 《译学辞典》. 上海:上海外语教育出版社. 2004. 冯翠华. 《英语修辞大全》,北京:外语教学与研究出版社, 1995. 冯庆华. 《文体与翻译》. 上海:上海外语教育出版社, 2002. 冯庆华主编. 《文体翻译论》. 上海:上海外语教育出版社. 2002. 冯胜利. 《汉语的韵律、词法与句法》. 北京:北京大学出版社, 1997. 冯志杰. 《汉英科技翻译指要》. 北京:中国对外翻译出版公司. 1998. 耿占春. 《隐喻》. 北京:东方出版社, 1993.

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