Adsorption thermodynamics and kinetic investigation of aromatic amphoteric compounds onto diffe
有机醇胺溶液选择性脱除H2S
Ni = kg P(yi − yi,int) = EkoL (xi,int − xi ) = KGP(yi − yi*)
(1)
通过阻力层方程将各传质系数关联起来：
1 KG
=
1 kg
+
1
HE
k
o L
(2)
通过准数群关联式Leveque 方程 Sh = aRe b Sc c 求出动力学参数kg和koL，关联式中常数a, b, c 由实验测定。表 2 和 3 列出了相关研究的气液传质面积的关联式和传质动力学关联式[6-13]。
湿壁柱反应器，圆盘反应器和膜接触器反应器具有确定的传质面积，其它反应器的传质面积
必须实验测定，通过关联式计算。
传质动力学取决于流体的物性、流体力学以及反应器结构，表征反应器传质动力学的参
数为气液传质速率（Ni），总体积传质系数（KGa, KLa）和总传质系数（KG, KL）等。设x和 y分别为组分i在液相和气相中的浓度，根据双膜理论模型，传质速率可表达为：
有机醇胺溶液选择性脱除H2S
陆建刚, 郑有飞
（南京信息工程大学环境科学与工程系，江苏南京 210044）
E-mail: jglu@
摘 要： H2S选择性脱除一直是气体净化领域的热点课题，本文较全面综述了有机醇胺溶液 选择性脱除H2S的特点和过程，着重分析了选择性脱除H2S过程中传质过程和动力学以及化学 反应机理等方面的研究，总结了有机醇胺溶液选择性脱除H2S技术的研究进展。 关键词：有机醇胺；H2S选择性脱除；技术进展
a / at
=
0.24(
L G
)0.25
Packed column
Random Roschig packing
硅烷偶联剂对二氧化钛表面改性
abstract
Due to their excellent photo-catalytic activities making TiO2 nanoparticles applicable as self-cleaning and anti-bacterial agents, as well as for UV protection and environmental purification, a great potential for multi-functionalization of fabrics by TiO2 nanoparticles is considered. In order to improve the durability of nanoparticles at a fabric surface, the surface of commercial TiO2 nanoparticles was modified by 3-aminopropyltrimethoxysilane (APTMS) and 3-Isocyanatopropyltrimethoxysilane (IPTMS) by an aqueous process in this study. The grafting efficiency of agents to TiO2 nanoparticles at different reaction conditions was estimated by thermal gravimetric analysis. FTIR spectra confirmed that organic functional groups were successfully grafted onto the TiO2 nanoparticles surface both for APTMS-grafted TiO2 nanoparticles (A-TiO2) and IPTMS-grafted TiO2 nanoparticles (I-TiO2) through Ti O Si chemical bonds. After the surface modification of TiO2 nanoparticles, isoelectric point (IEP) of nanoparticles was shifted approximately from pH 6.4 to pH 9.4 and the zeta potential plateaus increased significantly which was explained by the protonation of NH2 groups in the acidic region. The significant reduction of particle hydrodynamic diameters and polydispersity index (PDI) indicated the particle dispersion stability was positively affected by an increase in particle zeta potential. With increasing the organosilane ratio from 0 wt.% to 200 wt.%, a slight decline of the rate constant of A-TiO2 photocatalytic activity and a rapid decrease for I-TiO2 were revealed, which was significantly dependent on the grafting efficiency.
离子交换树脂吸附L-色氨酸的动力学研究
ｐ ｒｉｌ ａ ｔｒａ ｄ ａ ｓ ｒ ｔｏ ｅ ｅ ａｕ ｅ ｏ ｈ ｏ ｘｃ ａ ｇ ｒ ｅ ｓｗｅ ｅ ｉ ｖ ｓｉａｅ ．Ｔｈ ｅ ｕｌ ｈ ｗ ａｔｃｅ ｄｉｍｅｅ ｎ ｄ ｏ ｐ ｉ ｎ ｔｍｐ ｒｔ ｒ ｎ ｔ ｅ ｉ ｎ ｅ ｈ ｎ ｅ ｐ ｏｃ ｓ ｒ ｎ ｅ ｔｇ ｔ ｄ ｅｒｓ ｔ ｓ ｏ ｓ
第２ ６卷第 ４期 ２１ 年 ８月 ０２
高
校
化
学
工
程
学
报
ＮＯ ４ 、 １ ６ ． ， ． ０ ２
Ｊ ｕｎａ ｆ ｅ ｉａ ｎ ｎ ｅｉｇ ｏ ｉｅ ｅＵｎｉｅｓｔ ｓ ｏ ｒ ｌｏ ｍ ｃ ｌＥ ｇｉｅｒｎ ｆ Ｃｈ Ｃｈｎ ｓ ｖ ｒｉｉ ｅ
Ａｕ ． ２ ２ ｇ ０１
文章编号： １０ ．０ ５２ １ ）４０ １．６ ０ 附 Ｌ 色 氨 酸 的 动 力学 研 究 ．
谢友坪， 敬科举， 姚传 义， 卢英华
（ 门大学 化 学化 工学院 化 学工程与生物工程 系， 厦 福建 厦 门 ３ １ ０ ） ６０５
ｔａ ｔｅｍａ ｉ ｍ ｔ ｐｏ ｈ ｎ ａ ｓ ｒｔ ｎｃ ｐ ｃｔ ｆ ０ ７ｃ ｔ ｎｅ ｃ ａ ｇ ｅ ｉ ｎ ｒａｅ ｔ ｅ ｒａ ｉｇ ｈ ｔ ｈ ｘｍｕ Ｌ－ ｔｐ ａ ｄ ｏｐ ｉ ａ ａ ｉ ｏ ａｉ －ｘ ｈ ｎ ｅｒｓｎｉｃｅｓ ｓｗｉ ｄ ｃｅ ｓ ｙ ｒ ｏ ｙ ０１ ｏ ｘ ｈ ｎ
ｘＩ ｏ －ｉ ， ＪＮ ｅ ｕ Ｙ ＯＣ ｕｎｙ， Ｌ ｉ －ｕ ＥＹ ｕｐｎ ｇ Ｉ Ｇ Ｋ － ， Ａ ｈ ａ—ｉ ＵＹ ｎ ｈ ａ ｊ ｇ
（ ｐ ｒ ｎ ｆ ｅ ｃ ｌ ｎ ｏ ｈ ｍｉ ｌ ｎ ｉｅ ｒ ｇ Ｃｏｌ ｅｏ ｅ ｓ ｙａ ｄＣｈ ｍｉａ Ｅｎ ｉｅ ｒ ｇ Ｄｅ ａｔ ｔ ｍｉａ ａ ｄＢｉｃ ｅ ｃ ｇｎ ｅｉ ， ｌ ｇ ｆ ｍｅ ｏ Ｃｈ ａＥ ｎ ｅ Ｃｈ ｍｉｒ ｎ ｅ ｃ ｌ ｇｎ ｅｉ ， ｔ ｎ
水滑石焙烧产物对阴离子染料靛蓝胭脂红的吸附特性
水滑石焙烧产物对阴离子染料靛蓝胭脂红的吸附特性吴素花;李耀中【摘要】Calcined hydrotalcite is a potential adsorbent which can be used to remove anionic dyes from contaminated water. The adsorptive removal of indigo carmine,an anionic dye,from aqueous solution by calcined hydrotalcites with variable Mg/Al molar ratios was reported. Influences of calcination temperature,adsorbent dosage,initial dye concentration,initial pH and co-existing anions were investigated in a batch mode. The results indicate that CHTs prepared at 500 ℃ calcinatio n are most effective in removing indigo carmine with a removing rate higher than 95%. The adsorption capacity is found to be as high as 811. 5 mg/g (1. 74 mmol/g). Initial pH and co-existing anions have no impact on adsorption process. CHTs can be used to treat real printing and dyeing wastewater with a decolorization rate of 68% ~84%.%碳酸根型水滑石焙烧产物对阴离子染料具有特异的吸附性能。
溶剂热法制备磁性生物质炭吸附对硝基酚
DE引E言 对硝基苯酚为常见有机污染物"在环境中较难降
解"不仅对环境 造 成 污 染 " 同 时 也 对 人 体 健 康 产 生 危 害& 目前对硝基苯酚的处理方法主要有光催化降解 法 ($) ’M/)0-) 氧 化 法 (%) ’ 催 化 还 原 法 (!) 和 吸 附 法 (8I") 等 "其 中 吸 附 法 具 有 操 作 简 单 "能 耗 较 低 "实 现 废 物 回 收利用等优点"得到了广泛的应用&
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Elsevier期刊被SCI收录最新一期题录信息
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ISDS small-gain theorem and construction of ISDS Lyapunov functions for interconnected systemsPages 299-304Sergey Dashkovskiy, Lars Naujok7.An observer for a class of nonlinear systems with time varying observation delay Pages 305-312F. Cacace, A. Germani, C. Manes8.Rendezvous of multiple mobile agents with preserved network connectivity Pages 313-322Housheng Su, Xiaofan Wang, Guanrong ChenBiology（生物学）BIOELECTROCHEMISTRYVolume 79, Issue 1, Pages 1-152 (August 2010)1. Editorial BoardPage IFC2. ContentsPages v-vi3.Electrochemistry of norepinephrine on carbon-coated nickel magnetic nanoparticlesmodified electrode and analytical applicationsPages 1-5Chunli Bian, Qingxiang Zeng, Huayu Xiong, Xiuhua Zhang, Shengfu Wang4.Interaction of surface-attached haemoglobin with hydrophobic anions monitored by on-line acoustic wave detectorPages 6-10Jonathan S. Ellis, Steven Q. Xu, Xiaomeng Wang, Grégoi re Herzog, Damien W.M. 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Experimental flow field characteristics of OFA for large-angle counter flow of fuel-rich jet combustion technologyPages 2737-2745Weidong Fan, Zhengchun Lin, Youyi Li, Mingchuan ZhangEngineering, Electrical & Electronic（电机及电子工程）MICROELECTRONIC ENGINEERINGVolume 87, Issue 9, Pages 1655-1808 (November 2010)1. Inside Front Cover - Editorial BoardPage IFC2 PrefacePage 1655Joel Barnett3.In0.53Ga0.47As(1 0 0) native oxide removal by liquid and gas phase HF/H2O chemistriesPages 1656-1660F.L. Lie, W. Rachmady, A.J. Muscat4.A study of the interaction of gallium arsenide with wet chemical formulations using thermodynamic calculations and spectroscopic ellipsometryPages 1661-1664J. Price, J. Barnett, S. Raghavan, M. Keswani, R. Govindarajan5.The removal of nanoparticles from sub-micron trenches using megasonicsPages 1665-1668Pegah Karimi, Taehoon Kim, Juan Aceros, Jingoo Park, Ahmed A. Busnaina6.In-line control of Si loss after post ion implantation stripPages 1669-1673D. Shamiryan, D. Radisic, W. Boullart7.Removal of post-etch 193 nm photoresist in porous low-k dielectric patterning using UV irradiation and ozonated waterPages 1674-1679E. Kesters, Q.T. Le, M. Lux, L. Prager, G. Vereecke8.Repair of plasma-damaged p-SiOCH dielectric films in supercritical CO2Pages 1680-1684Jae Mok Jung, Hong Seok Kwon, Won-Ki Lee, Byung-Chun Choi, Hyun Gyu Kim, Kwon Taek Lim9.Development of compatible wet-clean stripper for integration of CoWP metal cap in Cu/low-k interconnectsPages 1685-1688Aiping Wu, Eugene Baryschpolec, Madhukar Rao, Matthias Schaller, Christin Bartsch, Susanne Leppack, Andreas Ott10.Dissolution and electrochemical impedance spectroscopy studies of thin copper oxide films on copper in semi-aqueous fluoride solutionsPages 1689-1695N. Venkataraman, S. Raghavan11.The sacrificial oxide etching of poly-Si cantilevers having high aspect ratios using supercritical CO2Pages 1696-1700Ha Soo Hwang, Jae Hyun Bae, Jae Mok Jung, Kwon Taek Lim12.Monitoring wafer cleanliness and metal contamination via VPD ICP-MS: Case studies for next generation requirementsPages 1701-1705Meredith Beebe, Scott Anderson13.Fabrication of a two-step Ni stamp for blind via hole application on PWB Pages 1707-1710In-Soo Park, Jin-Soo Kim, Seong-Hun Na, Seung-Kyu Lim, Young-Soo Oh, Su-Jeong Suh 14.Arrays of metallic nanocones fabricated by UV-nanoimprint lithographyPages 1711-1715Juha M. Kontio, Janne Simonen, Juha Tommila, Markus Pessa15.Synthesis, characterization of CeO2@SiO2 nanoparticles and their oxide CMP behaviorPages 1716-1720Xiaobing Zhao, Renwei Long, Yang Chen, Zhigang Chen16.Development of a triangular-plate MEMS tunable capacitor with linear capacitance–voltage responsePages 1721-1727M. Shavezipur, S.M. Hashemi, P. Nieva, A. Khajepour17.The correlation of the electrical properties with electron irradiation and constant voltage stress for MIS devices based on high-k double layer (HfTiSiO:N and HfTiO:N) dielectricsPages 1728-1734V. Mikhelashvili, P. Thangadurai, W.D. Kaplan, G. Eisenstein18. Intra-level voltage ramping-up to dielectric breakdown failure on Cu/porous low-k interconnections in 45 nm ULSI generationPages 1735-1740C.H. Huang, N.F. Wang, Y.Z. Tsai, C.I. Hung, M.P. Houng19. Anodic bonding of glass–ceramics to stainless steel coated with intermediate SiO2 layerPages 1741-1746Dehua Xiong, Jinshu Cheng, Hong Li, Wei Deng, Kai Ye20.Preparation of silica/ceria nano composite abrasive and its CMP behavior on hard disk substratePages 1747-1750Hong Lei, Fengling Chu, Baoqi Xiao, Xifu Tu, Hua Xu, Haineng Qiu21.Investigation on the controllable growth of monodisperse silica colloid abrasives for the chemical mechanical polishing applicationPages 1751-1755XiaoKai Hu, Zhitang Song, Haibo Wang, Weili Liu, Zefang Zhang22.Fabrication and electrical characteristics of ultrathin (HfO2)x(SiO2)1−x films by surface sol–gel method and reaction-anneal treatmentPages 1756-1759You-Pin Gong, Ai-Dong Li, Chao Zhao, Yi-Dong Xia, Di Wu23.Frequency properties of on-die power distribution network in VLSI circuits Pages 1760-1763Pavel Livshits, Yefim Fefer, Anton Rozen, Yoram Shapira24.Analytical modelling for the current–voltage characteristics of undoped or lightly-doped symmetric double-gate MOSFETsPages 1764-1768A. Tsormpatzoglou, D.H. Tassis, C.A. Dimitriadis, G. Ghibaudo, G. Pananakakis, N. Collaert25.Anti-buckling S-shaped vertical microprobes with branch springsPages 1769-1776Jung Yup Kim, Hak Joo Lee, Young-Ho Cho26.Characterization of UV photodetectors with MgxZn1−xO thin filmsPages 1777-1780Tung-Te Chu, Huilin Jiang, Liang-Wen Ji, Te-Hua Fang, Wei-Shun Shi, Tian-Long Chang, Teen-Hang Meen, Jingchang Zhong27.Barrier height temperature coefficient in ideal Ti/n-GaAs Schottky contacts Pages 1781-1784T. Göksu, N. Yıldırım, H. Korkut, A.F. Özdemir, A. Turut, A. Kökçe28.Optical coherence tomography for non-destructive investigation of silicon integrated-circuitsPages 1785-1791K.A. Serrels, M.K. Renner, D.T. Reid29.Materials selection procedure for RF-MEMSPages 1792-1795G. Guisbiers, E. Herth, B. Legrand, N. Rolland, T. Lasri, L. BuchaillotPreview PDF (303 K) | Related Articles30.Automated optical method for ultrasonic bond pull force estimationPages 1796-1804Henri Seppänen, Robert Schäfer, Ivan Kassamakov, Peter Hauptmann, Edward Hæggström31.Oxygen incorporation in TiN for metal gate work function tuning with a replacement gate integration approachPages 1805-1807Zilan Li, Tom Schram, Thomas Witters, Joshua Tseng, Stefan De Gendt, Kristin De MeyerEngineering, Industrial（工业工程）APPLIED ERGONOMICSVolume 41, Issue 5, Pages 643-718 (September 2010)1.Editorial BoardPage IFC2.Editorial for special issue of applied ergonomics on patient safetyPages 643-644Pascale Carayon, Peter Buckle3.Systems mapping workshops and their role in understanding medication errors in healthcarePages 645-656P. Buckle, P.J. Clarkson, R. Coleman, J. Bound, J. Ward, J. Brown4.Human factors in patient safety as an innovationPages 657-665Pascale Carayon5.Space to care and treat safely in acute hospitals: Recommendations from 1866 to 2008Pages 666-673Sue Hignett, Jun Lu6.Macroergonomics and patient safety: The impact of levels on theory, measurement, analysis and intervention in patient safety researchPages 674-681Ben-Tzion Karsh, Roger Brown7.Designing packaging to support the safe use of medicines at homePages 682-694James Ward, Peter Buckle, P. John Clarkson8.Reflective analysis of safety research in the hospital accident & emergency departmentsPages 695-700Robert L. Wears, Maria Woloshynowych, Ruth Brown, Charles A. Vincent9.Improving cardiac surgical care: A work systems approachPages 701-712Douglas A. Wiegmann, Ashley A. Eggman, Andrew W. ElBardissi, Sarah Henrickson Parker, Thoralf M. Sundt III10.Are hospitals becoming high reliability organizations?Pages 713-718Sebastiano Bagnara, Oronzo Parlangeli, Riccardo TartagliaEngineering, Civil(土木工程)ENGINEERING STRUCTURESVolume 32, Issue 7, Pages 1791-1956 (July 2010)1.A study of the collapse of a WWII communications antenna using numerical simulations based on design of experiments by FEMPages 1792-1800J.J. del Coz Díaz, P.J. García Nieto, A. Lozano Martínez-Luengas, J.L. Suárez Sierra 2.Evaluation study on structural fault of a Renaissance Italian palacePages 1801-1813Michele Betti, Gianni Bartoli, Maurizio Orlando3.Case study: Damage of an RC building after a landslide—inspection, analysis and retrofittingPages 1814-1820P. Tiago, E. Júlio4.Deep trench, landslide and effects on the foundations of a residential building:A case studyPages 1821-1829A. Brencich5.Forensic diagnosis of a shield tunnel failurePages 1830-1837Wei F. Lee, Kenji Ishihara6.Failure of concrete T-beam and box-girder highway bridges subjected to cyclic loading from trafficPages 1838-1845Kent K. Sasaki, Terry Paret, Juan C. Araiza, Peder Hals7.Durability problem of RC structures in Tuzla industrial zone — Two case studies Pages 1846-1860Radomir Folić, Damir Zenunović8.Transverse vibrations in existing railway bridges under resonant conditions: Single-track versus double-track configurationsPages 1861-1875M.D. Martínez-Rodrigo, J. Lavado, P. Museros9.Case study: Analytical investigation on the failure of a two-story RC building damaged during the 2007 Pisco-Chincha earthquakePages 1876-1887Oh-Sung Kwon, Eungsoo Kim10.An evaluation of effective design parameters on earthquake performance of RC buildings using neural networksPages 1888-1898M. Hakan Arslan11.Structural performance of the historic and modern buildings of the University of L’Aquila during the seismic events of April 2009Pages 1899-1924A.M. Ceci, A. Contento, L. Fanale, D. Galeota, V. Gattulli, M. Lepidi, F. Potenza14.Collapse modelling analysis of a precast soft storey building in Australia Pages 1925-1936。
纳米铁去除水体中镉的反应动力学、吸附平衡和影响因素
纳米铁去除水体中镉的反应动力学、吸附平衡和影响因素黄园英; 王倩; 汤奇峰; 刘久臣; 陈翠柏; 刘斯文【期刊名称】《《生态环境学报》》【年(卷),期】2019(028)010【总页数】9页(P2053-2061)【关键词】纳米铁; 镉离子去除; 吸附; 动力学; 平衡; 影响因素【作者】黄园英; 王倩; 汤奇峰; 刘久臣; 陈翠柏; 刘斯文【作者单位】国家地质实验测试中心北京 100037; 自然资源部生态地球化学重点实验室北京 100037; 中国地质大学水资源与环境学院北京 100083; 青岛聚创环保设备有限公司山东青岛 266043【正文语种】中文【中图分类】X132随着工业发展，大量重金属排入土壤及河流、湖泊和海洋等水体中，危害土壤、水生生态环境（Axtell et al.，2003；Amarasinghe et al.，2007；陈程等，2010）。
在这些重金属中，镉尤为突出。
镉（Cd）主要是通过石油燃烧、金属生产、磷肥施用、染料和液晶屏（Sharma，2008；Alloway et al.，1999；Perez-Marin et al.，2007）等途经进入环境中。
在我国，重金属已导致土壤和水严重污染。
Cd被列为人类致癌和致畸形物质，有研究表明Cd进入人体后首先造成对肾功能的损伤，进而引起肺、肝、骨、生殖器官的损伤，严重时可导致癌症的产生（Mahalik et al.，1995）。
世界卫生组织（WHO）规定饮用水中 Cd浓度不能超过0.003 mg·L-1（WHO，2008）。
由于Cd污染的普遍性和低的饮用水标准，所以必须发展一些技术去除污染水体中Cd。
目前，含镉废水实用处理技术包括化学沉淀法（邵红艳等，2018；常艳丽，2013）、铁氧体法（商娟等，2017；Wen et al.，2017）、离子交换法（车荣睿等，1994）、电絮凝法（孔茜，2009）、膜分离法（Mathilde，2004）、吸附法（符云聪等，2018；Qasemi et al.，2018）等。
戊二醛与羟基的交联机理
【研究】聚乙烯亚胺介孔二氧化硅和活性炭吸附CO2的热力学研究
在聚乙烯亚胺10k /中孔二氧化硅（PEI-10k / MPS）和活性炭（AC）上进行CO 2 吸附焓的热力学研究。
之所以选择这些材料是因为它们在PEI的约85℃和AC的约20℃下具有高CO 2吸附容量，因此可以在宽温度范围内高效捕获CO 2。
通过实验确定吸附的CO 2的绝对量作为在不同温度下的平衡压力的函数，并且分别拟合用于PEI和AC的广义Langmuir 和Toth方程的等温线。
CO的吸附2上PEI用温度揭示青睐该过程的吸热性质。
另一方面，AC上的CO 2吸附是放热的。
PEI上的等量吸附焓大致恒定，CO 2负载量为93kJ.mol -1，证实了其化学性质和Langmuir模型的确证。
相应的AC的等量焓在〜-25 kJ.mol -1范围内，随着CO 2的加载量不断下降; 确认该过程的物理吸附性质以及吸附层内的CO 2 / CO 2相互作用是显着的。
关键词等压吸附焓; 聚乙烯亚胺10k /中孔二氧化硅; 活性炭介绍CO水平升高2排放量已经沉淀了严重的环境问题。
CO的主要来源2排放量从天然气流茎和燃烧化石燃料，所以，除去CO的尝试2从这些来源已经获得广泛的兴趣[ 1 - 3 ]。
已经提出了用于从天然气流中捕集CO 2的各种技术技术。
这些技术包括不同的物理和化学程序，包括吸收，吸附，膜和低温。
由液体胺化学吸收是最适用的工业技术的CO 2洗涤[ 4，5]。
还使用了几种固体吸附剂。
一个子集基于无机- 有机杂化吸附剂[ 6 - 8 ]。
在大多数这些吸附剂，无机基材通常是在介孔形式，在那里它提供既大量的孔体积和大表面积上，并进入其中的活性有机基团掺入[ 9 - 12 ]。
使用至今最广泛的无机中孔载体是中孔二氧化硅[ 9 - 15 ]。
在这些吸附技术，捕获CO 2上胺固定在固体吸附剂已被认为是一个伟大的有前途的方法[ 16 - 19]。
到目前为止，固定在介孔二氧化硅（MPS）的胺已经显示出具有最高的CO 2吸附能力，高的解吸速率，疏忽的腐蚀问题，并在再生过程中的能量消耗低[ 18，19 ]。
Angew-2001-40-Noyori关于羰基的不对称氢化综述
1. Introduction
Catalysis plays a vital role in chemical synthesis. In particular, efficient molecular organometallic catalysis[1] provides a logical basis for molecular science and related technologies. Although selectivity, particularly in the control of absolute stereochemistry,[2, 3] is a major concern in modern organic synthesis, reactivity and productivity are also important in making reactions efficient and practical.[4, 5] A useful catalysis must show a high turnover number (TON), defined as mols of product per mol of catalyst, and a high turnover frequency (TOF), defined as TON per h or s. In addition, reactions should be operationally simple, safe, and
WILEY-VCH Verlag GmbH, D-69451 WeinheimS
theless, the ways to manipulate H2 chemically have remained limited. During our studies on homogeneous hydrogenation over two decades,[2, 9±11] our approaches and our choices, particularly chiral multiplication,[2] have been solely intuitive. Herein we describe the discovery and development of an uncommonly practical homogeneous hydrogenation process. The relative and absolute stereochemistry can be controlled efficiently and flexibly by molecular engineering. Prior to this, no general catalysts that effect selective ketone hydrogenation have existed.[10±13]
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．Ｃｏｌｌｅｇｅ ｏｆＥｎｖｉｒｏｎｍｅｎｔ，Ｎａｎｊｉｎｇ Ｕｎｉｖｅｒｓｉｔｙ ｏｆＴｅｃｈｎｏｌｏｇｙ，Ｎａｎｊｉｎｇ ２１０００９，Ｃｈｉｎａ．Ｅ—ｍａｉｌ：ｗａｎｇｈａｉｌｉｎｇ＠ｎｊｕ．ｏｒｇ．ｃｎ ２．Ｊｉａｎｇｓｕ Ｐｒｏｖｉｎｃｉａｌ Ｋｅｙ Ｌａｂｏｒａｔｏｒｙ ｏｆＣｏａｓｔａｌ Ｗｅｔｌａｎｄ Ｂｉｏｒｅｓｏｕｒｃｅｓ ａｎｄ Ｅｎｖｉｒｏｎｍｅｎｔａｌ Ｐｒｏｔｅｃｔｉｏｎ，Ｙａｎｃｈｅｎｇ ２２４００２，Ｃｈｉｎａ Ｓｔａｔｅ ＫｅｙＬａｂｏｒａｔｏｒｙｏｆＰｏｌｌｕｔｉｏｎ ＣｏｎｔｒｏｌａｎｄＲｅｓｏｕｒｃｅｓＲｅｕｓｅ，ＳｃｈｏｏｌｏｆＥｎｖｉｒｏｎｍｅｎｔ，Ｎａｎｊｉｎｇ Ｕｎｉｖｅｒｓｉｔｙ，Ｎａｎｊｉｎｇ２１００９３，Ｃｈｉｎａ
Ａｂｓｔｒａｃｔ Ｒｅｃｅｉｖｅｄ ２９ Ｊａｎｕａｒｙ ２００７；ｒｅｖｉｓｅｄ １２ Ａｐｒｉｌ ２００７；ａｃｃｅｐｔｅｄ １２ Ｍａｙ ２００７
Ｔｈｅ ａｄｓｏｒｐｔｉｏｎ ｂｅｈａｖｉｏｒ ｏｆｐ—ａｍｉｎｏｂｅｎｚｏｉｃ ａｃｉｄ ａｎｄ ｏ—ａｍｉｎｏｂｅｎｚｏｉｃ ａｃｉｄ ｏｎｔｏ ｔｈｅ ｄｉｆｆｅｒｅｎｔ ｐｏｌｙｍｅｒｉｃ ａｄｓｏｒｂｅｎｔｓ ｗａｓ ｓｙｓｔｅｍａｔｉｃａｌｌｙ ｉｎｖｅｓｔｉｇａｔｅｄ ａｓ ａ ｆｕｎｃｔｉｏｎ ｏｆ ｔｈｅ ｓｏｌｕｔｉｏｎ ｃｏｎｃｅｎｔｒａｔｉｏｎ ａｎｄ ｔｅｍｐｅｒａｔｕｒｅ．Ｅｘｐｅｒｉｍｅｎｔａｌ ｒｅｓｕｌｔｓ ｉｎｄｉｃａｔｅｄ ｔｈａｔ ｔｈｅ ｅｑｕｉｌｉｂｒｉｕｍ ａｄｓｏｒｐｔｉｏｎ ｄａｔａ ｏｆ ｔｈｅ ｆｏｕｒ ｐｏｌｙｍｅｒｉｃ ａｄｓｏｒｂｅｎｔｓ ｆｉｔｔｅｄ ｗｅｌｌ ｉｎ ｔｈｅ Ｆｒｅｕｎｄｌｉｃｈ ｉｓｏｔｈｅｒｍ．Ｔｈｅ ａｄｓｏｒｐｔｉｏｎ ｃａｐａｃｉｔｙ ｏｆ ｍｕｌｔｉ—ｆｕｎｃｔｉｏｎａｌ ｐｏｌｙｍｅｒｉｃ ａｄｓｏｒｂｅｎｔ ＮＪ一９９ ｗａｓ ｔｈｅ ｈｉｇｈｅｓｔ．ｗｈｉｃｈ ｍｉｇｈｔ ｂｅ ａｔｔｒｉｂｕｔｅｄ ｔｏ ｔｈｅ ｓｔｒｏｎｇ ｈｙｄｒｏｇｅｎ—ｂｏｎｄｉｎｇ ｉｎｔｅｒａｃｔｉｏｎ ｂｅｔｗｅｅｎ ｔｈｅ ａｍｉｎｏ ｇｒｏｕｐｓ ｏｎ ｔｈｅ ｒｅｓｉｎ ａｎｄ ｔｈｅ ｃａｒｂｏｘｙｌ ｇｒｏｕｐ ｏｆ ａｍｉｎｏｂｅｎｚｏｉｃ ａｃｉｄ．Ｔｈｅ ａｄｓｏｒｐｔｉｏｎ ｃａｐａｃｉｔｙ ｏｆ ｏ—ａｍｉｎｏｂｅｎｚｏｉｃ ａｃｉｄ ｏｎｔｏ ａｎｙ ａｄｓｏｒｂｅｎｔ ｗａｓ ｈｉｇｈｅｒ ｔｈａｎ Ｐ—ａｍｉｎｏｂｅｎｚｏｉｃ ａｃｉｄ．Ｔｈｅｒｍｏｄｙｎａｍｉｃ ｓｔｕｄｉｅｓ ｓｕｇｇｅｓｔｅｄ ｔｈｅ ｅｘｏｔｈｅｒｍｉｃ，ｓｐｏｎｔａｎｅｏｕｓ ｐｈｙｓｉｃａｌ ａｄｓｏｒｐｔｉｏｎ ｐｒｏｃｅｓｓ．Ａｄｓｏｒｐｔｉｏｎ ｋｉｎｅｔｉｃｓ ｒｅｓｕｌｔｓ ｓｈｏｗｅｄ ｔｈａｔ ｔｈｅ ａｄｓｏｒｐｔｉｏｎ ｆｏｌｌｏｗｅｄ ｔｈｅ ｐｓｅｕｄｏ—ｓｅｃｏｎｄ．ｏｒｄｅｒ ｋｉｎｅｔｉｃｓ ｍｏｄｅｌ ａｎｄ ｔｈｅ ｉｎｔｒａｐａｒｔｉｃｌｅ ｍａｓｓ ｔｒａｎｓｆｅｒ ｐｒｏｃｅｓｓ ｗａｓ ｔｈｅ ｒａｔｅ—ｃｏｎｔｒｏｌｌｉｎｇ ｓｔｅｐ．
Ｋｅｙ ｗｏｒｄｓ：ａｒｏｍａｔｉｃ ａｍｐｈｏｔｅｒｉｃ ｃｏｍｐｏｕｎｄ；ａｍｉｎｏｂｅｎｚｏｉｃ ａｃｉｄ；ｐｏｌｙｍｅｒｉｃ ａｄｓｏｒｂｅｎｔｓ；ａｄｓｏｒｐｔｉｏｎ；ｔｈｅｒｍｏｄｙｎａｍｉｃｓ；ｋｉｎｅｔｉｃｓ
ＩｎｔｒＯｄｕｃｔｉＯｎ Ｗａｓｔｅｗａｔｅｒ ｃｏｎｔａｉｎｉｎｇ ａｒｏｍａｔｉｃ ｃｏｍｐｏｕｎｄｓ ｐｒｅｓｅｎｔｓ ａ ｓｅｒｉｏｕｓ ｄｉｓｐｏｓａｌ ｐｒｏｂｌｅｍ ｂｅｃａｕｓｅ ｏｆ ｉｔｓ ｔｏｘｉｃｉｔｙ ａｎｄ ｐｏｏｒ ｂｉｏｄｅｇｒａｄａｔｉｏｎ ａｓ ｗｅｌｌ ａｓ ｇｏｏｄ ｓｏｌｕｂｉｌｉｔｙ ｉｎ ｗａｔｅｒ．Ｅｓｐｅ— ｃｉａｌｌｙ ｆｏｒ ｔｈｅ ａｒｏｍａｔｉｃ ａｍｐｈｏｔｅｒｉｃ ｃｏｍｐｏｕｎｄｓ ｉｎｖｏｌｖｉｎｇ ｂｏｔｈ Ｌｅｗｉｓ ａｃｉｄ ａｎｄ Ｌｅｗｉｓ ｂａｓｅ ｆｕｎｃｔｉｏｎａｌ ｇｒｏｕｐｓ．ｔｈｅｉｒ ｐａｒｔｉｃｕｌａｒ ｐｈｙｓｉｃｏｃｈｅｍｉｃａｌ ｃｈａｒａｃｔｅｒｉｓｔｉｃｓ ｂｒｉｎｇ ｍｏｒｅ ｄｉｆ＿ ｆｉｃｕｌｔｉｅｓ ｆｏｒ ｔｈｅ ｔｒｅａｔｍｅｎｔ ｏｆ ｗａｓｔｅｗａｔｅｒ．Ａ ｌｏｔ ｏｆ ｍｅｔｈｏｄｓ． ｓｕｃｈ ａｓ ｂｉｏｌｏｇｉｃａｌ ｄｅｇｒａｄａｔｉｏｎ ａｎｄ ｏｘｉｄａｔｉｏｎ（Ｚｈａｎｇ ｅｔ ａ１．，１９９９；Ｌｉｎ ｅｔ ａ１．，２００１），ａｐｐｌｉｅｄ ｆｏｒ ｔｈｅ ｐｕｒｉｆｉｃａｔｉｏｎ ｏｆ ｗａｔｅｒ ｃｏｎｔａｍｉｎａｔｅｄ ｂｙ ａｒｏｍａｔｉｃ ａｍｐｈｏｔｅｒｉｃ ｃｏｍｐｏｕｎｄｓ， ａｒｅ ｏｆｔｅｎ ｗｉｔｈ ｌｉｍｉｔｅｄ ｓｕｃｃｅｓｓ．Ｒｅｓｉｎ ａｄｓｏｒｐｔｉｏｎ ｔｅｃｈｎｏｌ— ｏｇｙ ｈａｓ ｂｅｅｎ ｕｓｅｄ ａｓ ａ ｍｏｒｅ ａｔｔｒａｃｔｉｖｅ ａｌｔｅｒｎａｔｉｖｅ ｆｏｒ ｒｅｍｏｖｉｎｇ ａｒｏｍａｔｉｃ ｐｏｌｌｕｔａｎｔｓ ｆｒｏｍ ｗａｓｔｅｗａｔｅｒ（Ｈｅ ａｎｄ Ｈｕａｎｇ，１９９５；Ｚｈａｎｇ ｅｔ ａ１．，２００１）．Ｍａｎｙ ｓｔｕｄｉｅｓ ｆＰａｎ ｅｔ ａ１．，２００５；Ｃａｉ ｅｔ ａ１．，２００５）ｈａｖｅ ｂｅｅｎ ｃｏｎｄｕｃｔｅｄ ｏｎ ｔｈｅ ｒｅｍｏｖａｌ ｏｆ ｐｈｅｎｏｌｓ ａｎｄ ａｒｏｍａｔｉｃ ａｍｉｎｅｓ ｉｎｖｏｌｖｉｎｇ ｏｎｅ ｎｄ ｏｆ ｆｕｎｃｔｉｏｎａｌ ｇｒｏｕｐ．Ｈｏｗｅｖｅｒ，ｔｈｅ ｃｏｎｃｅｒｎｅｄ ｒｅｓｅａｒｃｈ ｏｎ ｔｈｅ ｒｅｓｉｎ ａｄｓｏｒｐｔｉｏｎ ｔｅｃｈｎｉｑｕｅｓ ｏｆ ａｒｏｍａｔｉｃ ａｍｐｈｏｔｅｒｉｃ ｃｏｍｐｏｕｎｄｓ ｈａｓ ｎｏｔ ｂｅｅｎ ｓｙｓｔｅｍａｔｉｃａｌｌｙ ｉｎｖｅｓｔｉｇａｔｅｄ． ＭａＳＳ ｔｒａｎｓｆｅｒ ｗｉｔｈｉｎ ｔｈｅ ｒｅｓｉｎ ｐａｒｔｉｃｌｅｓ ｃａｎ ｂｅ ｃｏｍｐｌｅｘ，
Ｐｒｏｊｅｃｔ ｓｕｐｐｏｒｔｅｄ ｂｙ出ｅ Ｎａｔｉｏｎａｌ Ｋｅｙ Ｔｅｃｈｎｏｌｏｇｙ Ｒｅｓｅａｒｃｈ ａｎｄ Ｄｅｖｅｌｏｐｍｅｎｔ Ｐｒｏｇｒａｍ ｏｆ Ｃｈｉｎａ（Ｎｏ．２００６ＢＡＣ０２Ａ１５），ｔｈｅ Ｏｐｅｎｉｎｇ Ｆｏｕｎｄａｔｉｏｎ ｏｆ Ｊｉａｎｇｓｕ Ｐｒｏｖｉｎｃｉａｌ Ｋｅｙ Ｌａｂｏｒａｔｏｒｙ ｏｆ Ｃｏａｓｔａｌ Ｗｅｔｌａｎｄ Ｂｉｏｒｅｓｏｕｒｃｅｓ ａｎｄ Ｅｎｖｉｒｏｎｍｅｎｔａｌ Ｐｒｏｔｅｃｔｉｏｎ ｏｆ Ｃｈｉｎａ（Ｎｏ．ＪＬＣＢＥ０５０ｏ６１ ａｎｄ出ｅ Ｑｉｎｇｌａｎ Ｐｒｏｊｅｃｔ ｏｆ Ｊｉａｎｇｓｕ Ｐｒｏｖｉｎｃｅ．＊Ｃｏｒｒｅｓｐｏｎｄｉｎｇ ａｎ出ｏｒ． Ｅ—ｍａｉｌ：ｗａｎｇｈａｉｌｉｎｇ＠ｎｊｕ．ｏｒｇ．ｃｎ．
ａｓ ａｄｓｏｒｐｔｉｏｎ ｉｓ ｉｎｈｅｒｅｎｔｌｙ ａ ｔｒａｎｓｉｅｎｔ ｐｒｏｃｅｓｓ ｉｎｖｏｌｖｉｎｇ ｓｏｍｅ ｓｈｏｒｔ．ｒａｎｇｅ ｄｉｆｌｕｓｉｏｎ ｉｎ ｂｏｔｈ ｔｈｅ ｆｌｕｉｄ ａｎｄ ｔｈｅ ａｄ— ｓｏｒｂｅｄ ｐｈａｓｅｓ．Ｂｏｔｈ ｉｎｔｒａｐａｒｔｉｃｌｅ ａｎｄ ｅｘｔｅｒｎａｌ ｄｉｆｌｕｓｉｏｎ ｍａｙ ｐｌａｙ ａ ｒｏｌｅ ｉｎ ｔｈｅ ｌｉｑｕｉｄ ｐｈａｓｅ ａｄｓｏｒｐｔｉｏｎ ｏｎ ｐｏｒｏｕｓ ａｄｓｏｒｂｅｎｔｓ．Ａｌｔｈｏｕｇｈ ａ ｌａｒｇｅ ｎｕｍｂｅｒ ｏｆ ｓｔｕｄｉｅｓ ｏｎ ｔｈｅ ａｄｓｏｒｐｔｉｏｎ ｋｉｎｅｔｉｃｓ ｈａｖｅ ｂｅｅｎ ｒｅｐｏｒｔｅｄ（Ａｎｎａｄｕｒａｉ ａｎｄ Ｋｒｉｓｈｎａｎ，１９９７；Ｈｏ ａｎｄ Ｍｃｋａｙ，１９９９；Ｍｃｋａｙ ａｎｄ Ｈｏ， １ ９９９；Ｌｉ ａｎｄ Ａｒｕｐ，２０００），ｆｅｗ ｏｆ ｔｈｅｍ ａｄｄｒｅｓｓｅｄ ｔｈｅ
ａｄｓｏｒｐｔｉｏｎ ｔｈｅｒｍｏｄｙｎａｍｉｃｓ ａｎｄ ｋｉｎｅｔｉｃｓ ｏｆ ａｒｏｍａｔｉｃ ａＦｆｌ— ｐｈｏｔｅｒｉｃ ｃｏｍｐｏｕｎｄｓ ｏｎ ｐｏｌｙｍｅｒｉｃ ａｄｓｏｒｂｅｎｔｓ． Ｔｈｅ ｃｕｒｒｅｎｔ ｓｔｕｄｙ ａｉｍｅｄ ａｔ ｉｄｅｎｔｉｆｙｉｎｇ ｔｈｅ ｓｉｇｎｉｆｉｃａｎｃｅ ｏｆ ｉｎｔｒａｐａｒｔｉｃｌｅ ａｎｄ ｅｘｔｅｒｎａｌ ｄｉｆｌｕｓｉｏｎ ｏｆ ｔｈｅ ａｒｏｍａｔｉｃ ａｍｐｈｏｔｅｒｉｃ ｃｏｍｐｏｕｎｄ ａｍｉｎｏｂｅｎｚｏｉｃ ａｃｉｄ ｉｎｓｉｄｅ ｔｈｅ ｗａｔｅｒ－ ｃｏｍｐａｔｉｂｌｅ ｈｙｐｅｒｃｒｏｓｓｌｉｎｋｅｄ ｍｕｌｔｉ—ｆｕｎｃｔｉｏｎａｌ ｐｏｌｙｍｅｒｉｃ ａｄｓｏｒｂｅｎｔ ＮＪ．９９ ａｎｄ ＮＧ．１ ０ ｉｎ ｃｏｍｐａｒｉｓｏｎ ｗｉｔｈ ｔｈｅ ｈｙ． ｐｅｒｃｒｏｓｓｌｉｎｋｅｄ ａｄｓｏｒｂｅｎｔ ＣＨＡ一１ １ １ ａｎｄ ｔｈｅ ｈｙｄｒｏｐｈｏｂｉｃ ｍａｃｒｏｐｏｒｏｕｓ ａｄｓｏｒｂｅｎｔ ＸＡＤ．４．Ｔｈｅｒｍｏｄｙｎａｍｉｃ ｉｎｖｅｓｔｉ． ｇａｔｉｏｎｓ ｈａｖｅ ｂｅｅｎ ｐｅｒｆｏｒｍｅｄ ｔｏ ｅｌｕｃｉｄａｔｅ ｔｈｅ ｅｑｕｉｌｉｂｒｉｕｍ ａｄｓｏｒｐｔｉｏｎ ｂｅｈａｖｉｏｒ ｏｆ ａｍｉｎｏｂｅｎｚｏｉｃ ａｃｉｄ ｏｎｔｏ ｐｏｌｙｍｅｒｉｃ ａｄｓｏｒｂｅｎｔｓ．
１ Ｍａｔｅｒｉａｌｓ ａｎｄ ｍｅｔｈｏｄｓ １．１ Ｍａｔｅｒｉａｌｓ Ｔｗｏ ｋｉｎｄｓ ｏｆ ａｍｉｎｏｂｅｎｚｏｉｃ ａｃｉｄ —ａｍｉｎｏｂｅｎｚｏｉｃ ａｃｉｄ ａｎｄ ｏ—ａｍｉｎｏｂｅｎｚｏｉｃ ａｃｉｄ１ ｗｅｒｅ ｐｕｒｃｈａｓｅｄ ｆｒｏｍ Ｓｈａｎｇｈａｉ