一步法合成微-介孔多级孔道金属-有机骨架固载磷钨酸催化剂及其催化性能

引用本文: 杨新丽, 乔丽明, 戴维林. 一步法合成微-介孔多级孔道金属-有机骨架固载磷钨酸催化剂及其催化性能[J]. 催化学报, 2015, 36(11): 1875-1885. doi: 10.1016/S1872-2067(15)60972-X shu

Citation: Xinli Yang, Liming Qiao, Weilin Dai. One-pot synthesis of a hierarchical microporous-mesoporous phosphotungstic acid-HKUST-1 catalyst and its application in the selective oxidation of cyclopentene to glutaraldehyde[J]. Chinese Journal of Catalysis, 2015, 36(11): 1875-1885. doi: 10.1016/S1872-2067(15)60972-X shu

一步法合成微-介孔多级孔道金属-有机骨架固载磷钨酸催化剂及其催化性能

杨新丽 ^{a,
,} ,
乔丽明 ^a, ,
戴维林 ^{b,
,}

通讯作者: 戴维林. 电话: (021)55664678; 传真: (021)55665701; 电子信箱: wldai@fudan.edu.cn;杨新丽. 电话: (0371)67756193; 传真: (0371)67756718; 电子信箱: xlyang@haut.edu.cn; 戴维林. 电话: (021)55664678; 传真: (021)55665701; 电子信箱: wldai@fudan.edu.cn;杨新丽. 电话: (0371)67756193; 传真: (0371)67756718; 电子信箱: xlyang@haut.edu.cn

基金项目:
河南工业大学自然科学基础研究重点培育计划(2013JCYJ09) (2013JCYJ09)

河南省省属高校基本科研业务费专项资金(2014YWQQ13) (2014YWQQ13)

国家自然科学基金(20903035, 21373054). (20903035, 21373054)

摘要: 磷钨酸具有酸性, 而且具有氧化还原性, 是一种多功能的新型催化剂, 具有很高的催化活性, 稳定性好, 既可作均相催化剂, 也可做多相催化剂. 磷钨酸作为多相催化剂主要负载于无机氧化物、介孔分子筛、活性炭和离子交换树脂等材料中, 然而这些多相催化剂存在着结构不明确, 磷钨酸分散不均、易流失、活性点易中毒等问题. 为了克服以上问题, 需要寻找更加合适的载体来制备新颖的负载型的磷钨酸多相催化剂, 金属-有机骨架的独特性质, 使该材料成为一种优良的催化剂载体. 金属-有机骨架(MOFs)又称配位聚合物, 是指由金属离子与有机配体通过配位键和其他一些弱作用力连接而成的具有超分子微孔网络结构的一种颇具应用前途的类沸石材料. 这种材料具有丰富的孔结构和很大的比表面积, 同时具有孔结构规整、孔径大小设计可调、表面化学基团修饰可调等优点, 使得它在吸附分离、多相催化、环境保护等领域具有很好的应用前景. HKUST-1 (Cu-BTC或MOF-199)是该领域内研究和应用较多的一种金属-有机骨架材料, 它最早由香港大学Williams教授课题组报道, 其为面心立方晶体. 在结构中, 每个Cu₂簇与四个均苯三甲酸相连, 每个均苯三甲酸桥连着三个Cu₂簇, 形成轮浆式次级结构单元. 这些次级结构单元相互交错连接形成3D网络结构, 具有孔径约为0.9 nm × 0.9 nm的正方形孔道, 孔道中的客体分子可以除去, 并可以为其它的客体分子所置换. HKUST-1本身即是一种优良的催化剂, 同时也可作为一种性能稳定的催化剂载体. 目前, 关于HKUST-1在催化领域中的应用主要限制在微孔范围, 其较小的孔道不利于物质扩散和传输, 从而限制其实际应用.
本论文利用超分子模板法, 以十六烷基三甲基溴化铵(CTAB)为模板剂、铜为金属中心、均苯三甲酸为有机配体、磷钨酸(HPWs)为活性组分, 采用一步水热法合成微-介孔多级孔道金属-有机骨架固载磷钨酸催化剂HPWs@Meso-HKUST-1, 详细研究了该催化剂对环戊烯选择氧化制备戊二醛的催化性能, 并采用X射线粉末衍射(XRD)、傅里叶红外光谱(FT-IR)、N₂吸附、透射电镜(TEM)和室温CO原位吸附红外(CO-FT-IR)等表征手段对HPWs@Meso-HKUST-1催化剂进行了结构表征, 从而解释该催化剂对目标反应具有优良催化性能的本质原因.
N₂吸附表征结果说明, HPWs@Meso-HKUST-1催化剂的吸附-脱附曲线在低相对压力范围内呈现I型吸附等温线, 在高相对压力范围内呈现具有H2型滞后环的IV型吸附等温线; 催化剂独特的吸附等温线表明以CTAB为模板剂, 采用一步水热合成法可以得到具有微孔和介孔多级孔道的催化剂材料. 催化剂的比表面积和孔容随着磷钨酸含量的增加而减少, 结合文献报道, 可以得出一步水热合成法使活性组分HPWs分布在载体的介孔孔道内. XRD和FT-IR测试结果表明, 一步水热合成法可以成功的将HPWs引入HKUST-1中, 且HPWs高度分散在载体中; HPWs@Meso-HKUST-1催化剂保持了载体HKUST-1的骨架结构. 小角XRD和TEM结果说明, 催化剂的多级孔结构为无序蠕虫状介孔组织. 室温CO-FT-IR说明, 在HPWs@Meso-HKUST-1催化剂中, HPWs提供了不同于载体HKUST-1的L酸酸性位. 从以上结果可以得出, 一步水热合成法使HPWs包裹在载体的介孔孔道内, 防止了HPWs的流失, 使HPWs@Meso-HKUST-1催化剂为环戊烯选择氧化制备戊二醛提供了大量的、高度分散的、具有L酸酸性位的活性中心, 且催化剂的介孔孔道有利于反应物和产物的扩散, 从而使该催化剂表现出优良的催化性能; 在优化条件下, 环戊烯的转化率达到92.5%, 戊二醛的得率达到78.9%; 热过滤实验表明该催化剂是真正的多相催化剂, 且至少可以重复使用3次.

关键词:

English

One-pot synthesis of a hierarchical microporous-mesoporous phosphotungstic acid-HKUST-1 catalyst and its application in the selective oxidation of cyclopentene to glutaraldehyde

Xinli Yang ^{a,
,} ,
Liming Qiao ^a, ,
Weilin Dai ^{b,
,}

1.
a School of Chemistry & Chemical Engineering, Henan University of Technology, Zhengzhou 450001, Henan, China;

Corresponding author: 戴维林. 电话: (021)55664678; 传真: (021)55665701; 电子信箱: wldai@fudan.edu.cn;杨新丽. 电话: (0371)67756193; 传真: (0371)67756718; 电子信箱: xlyang@haut.edu.cn; 戴维林. 电话: (021)55664678; 传真: (021)55665701; 电子信箱: wldai@fudan.edu.cn;杨新丽. 电话: (0371)67756193; 传真: (0371)67756718; 电子信箱: xlyang@haut.edu.cn

Received Date: 15 July 2015
Fund Project:
河南工业大学自然科学基础研究重点培育计划(2013JCYJ09)

河南省省属高校基本科研业务费专项资金(2014YWQQ13)

国家自然科学基金(20903035, 21373054).

Abstract: A hierarchical microporous-mesoporous metal-organic framework of HKUST-1(Cu)-encapsulated phosphotungstic acid (HPW) material, referred to as HPWs@Meso-HKUST-1, is prepared by a one-pot synthesis method using cetyltrimethylammonium bromide as the supramolecular template. The addition of HPWs to the synthesis mixture of hierarchical porous HKUST-1 results in the direct encapsulation of HPWs inside the mesopores of the HKUST-1 structure, with a homogeneous distribution over the HKUST-1 crystals, which is confirmed by XRD, FT-IR, N₂ adsorption, UV-Vis DRS, and TEM. FT-IR-CO adsorption experiments indicated that additional Lewis acid sites were present in the HPWs@Meso-HKUST-1 sample. The novel heterogeneous catalyst demonstrates excellent catalytic performance for the selective oxidation of cyclopentene (CPE) to glutaraldehyde (GA) using tert-butyl hydroperoxide and acetonitrile (MeCN) as the oxidant and solvent, respectively. The high activity of the catalyst is attributed to the mesostructure of the catalyst and the nature and appropriate abundance of the HPWs—being highly dispersed with the addition of Lewis sites. After a reaction for 36 h, the 30% wt% HPWs@Meso-HKUST-1 catalyst exhibits a CPE conversion of 92.5% and a high GA yield of 73%. Furthermore, the HPWs@Meso-HKUST-1 material is sufficiently stable to prevent the leaching of HPWs, and behaves as a true heterogeneous catalyst that can be repeatedly recycled without sustaining a loss of activity and selectivity in the selective oxidation of CPE.

Key words:

1. [1] Kozhevnikov I V. Chem Rev, 1998, 98: 171[1] Kozhevnikov I V. Chem Rev, 1998, 98: 171
2. [2] Inumaru K, Ishihara T, Kamiya Y, Okuhara T, Yamanaka S. Angew Chem Int Ed, 2007, 46: 7625[2] Inumaru K, Ishihara T, Kamiya Y, Okuhara T, Yamanaka S. Angew Chem Int Ed, 2007, 46: 7625
3. [3] Bigi F, Corradini A, Quarantelli C, Sartori G. J Catal, 2007, 250: 222[3] Bigi F, Corradini A, Quarantelli C, Sartori G. J Catal, 2007, 250: 222
4. [4] Khder A E R S. Appl Catal A, 2008, 343: 109[4] Khder A E R S. Appl Catal A, 2008, 343: 109
5. [5] Schwegler M A, Vinke P, van der Eijk M, van Bekkum H. Appl Catal A, 1992, 80: 41[5] Schwegler M A, Vinke P, van der Eijk M, van Bekkum H. Appl Catal A, 1992, 80: 41
6. [6] Dupont P, Védrine J C, Paumard E, Hecquet G, Lefebvre F. Appl Catal A, 1995, 129 : 217[6] Dupont P, Védrine J C, Paumard E, Hecquet G, Lefebvre F. Appl Catal A, 1995, 129 : 217
7. [7] Nomiya K, Murasaki H, Miwa M. Polyhedron, 1986, 5: 1031[7] Nomiya K, Murasaki H, Miwa M. Polyhedron, 1986, 5: 1031
8. [8] Kozhevnikov I V, Kloetstra K R, Sinnema A, Zandbergen H W, van Bekkum H. J Mol Catal A, 1996, 114: 287[8] Kozhevnikov I V, Kloetstra K R, Sinnema A, Zandbergen H W, van Bekkum H. J Mol Catal A, 1996, 114: 287
9. [9] Yuan C Y, Chen J. Chin J Catal (袁程远, 陈静. 催化学报), 2011, 32: 1191[9] Yuan C Y, Chen J. Chin J Catal (袁程远, 陈静. 催化学报), 2011, 32: 1191
10. [10] Khder A E R S, Khder, Hassan H M A, El-Shall M S. Appl Catal A, 2012, 411-412: 77[10] Khder A E R S, Khder, Hassan H M A, El-Shall M S. Appl Catal A, 2012, 411-412: 77
11. [11] Ferey G. Chem Soc Rev, 2008, 37: 191[11] Ferey G. Chem Soc Rev, 2008, 37: 191
12. [12] Long J R, Yaghi O M. Chem Soc Rev, 2009, 38: 1213[12] Long J R, Yaghi O M. Chem Soc Rev, 2009, 38: 1213
13. [13] Dhakshinamoorthy A, Garcia H. Chem Soc Rev, 2012, 41: 5262[13] Dhakshinamoorthy A, Garcia H. Chem Soc Rev, 2012, 41: 5262
14. [14] Prestipino C, Regli L, Vitillo J G, Bonino F, Damin A, Lamberti C, Zecchina A, Solari P L, Kongshaug K O, Bordiga S. Chem Mater, 2006, 18: 1337[14] Prestipino C, Regli L, Vitillo J G, Bonino F, Damin A, Lamberti C, Zecchina A, Solari P L, Kongshaug K O, Bordiga S. Chem Mater, 2006, 18: 1337
15. [15] Chui S S Y, Lo S M F, Charmant J P H, Orpen A G, Williams I D. Science, 1999, 283: 1148[15] Chui S S Y, Lo S M F, Charmant J P H, Orpen A G, Williams I D. Science, 1999, 283: 1148
16. [16] Schlichte K, Kratzke T, Kaskel S. Microporous Mesoporous Mater, 2004, 73: 81[16] Schlichte K, Kratzke T, Kaskel S. Microporous Mesoporous Mater, 2004, 73: 81
17. [17] Alaerts L, Séguin E, Poelman H, Thibault-Starzyk F, Jacobs P A, De Vos D E. Chem Eur J, 2006, 12: 7353[17] Alaerts L, Séguin E, Poelman H, Thibault-Starzyk F, Jacobs P A, De Vos D E. Chem Eur J, 2006, 12: 7353
18. [18] Dhakshinamoorthy A, Alvaro M, Garcia H. J Catal, 2009, 267: 1[18] Dhakshinamoorthy A, Alvaro M, Garcia H. J Catal, 2009, 267: 1
19. [19] Wu Y, Qiu L G, Wang W, Li Z Q, Xu T, Wu Z Y, Jiang X. Trans Met Chem, 2009, 34: 263[19] Wu Y, Qiu L G, Wang W, Li Z Q, Xu T, Wu Z Y, Jiang X. Trans Met Chem, 2009, 34: 263
20. [20] Brown K, Zolezzi S, Aguirre P, Venegas-Yazigi D, Paredes-Garcia V, Baggio R, Novak M A, Spodine E. Dalton Trans, 2009: 1422[20] Brown K, Zolezzi S, Aguirre P, Venegas-Yazigi D, Paredes-Garcia V, Baggio R, Novak M A, Spodine E. Dalton Trans, 2009: 1422
21. [21] Marx S, Kleist W, Baiker A. J Catal, 2011, 281: 76[21] Marx S, Kleist W, Baiker A. J Catal, 2011, 281: 76
22. [22] Sun C Y, Liu S X, Liang D D, Shao K Z, Ren Y H, Su Z M. J Am Chem Soc, 2009, 131: 1883[22] Sun C Y, Liu S X, Liang D D, Shao K Z, Ren Y H, Su Z M. J Am Chem Soc, 2009, 131: 1883
23. [23] Janssens N, Wee L H, Bajpe S, Breynaert E, Kirschhock C E A, Martens J A. Chem Sci, 2012, 3: 1847[23] Janssens N, Wee L H, Bajpe S, Breynaert E, Kirschhock C E A, Martens J A. Chem Sci, 2012, 3: 1847
24. [24] Song J, Luo Z, Britt D K, Furukawa H, Yaghi O M, Hardcastle K I, Hill C L. J Am Chem Soc, 2011, 133: 16839[24] Song J, Luo Z, Britt D K, Furukawa H, Yaghi O M, Hardcastle K I, Hill C L. J Am Chem Soc, 2011, 133: 16839
25. [25] Yang H, Li J, Wang L Y, Dai W, Lü Y, Gao S. Catal Commun, 2013, 35: 101[25] Yang H, Li J, Wang L Y, Dai W, Lü Y, Gao S. Catal Commun, 2013, 35: 101
26. [26] Wee L H, Janssens N, Bajpe S R, Kirschhock C E A, Martens J A. Catal Today, 2011, 171: 275[26] Wee L H, Janssens N, Bajpe S R, Kirschhock C E A, Martens J A. Catal Today, 2011, 171: 275
27. [27] Klein N, Senkovska I, Gedrich K, Stoeck U, Henschel A, Mueller U, Kaskel S. Angew Chem Int Ed, 2009, 48: 9954[27] Klein N, Senkovska I, Gedrich K, Stoeck U, Henschel A, Mueller U, Kaskel S. Angew Chem Int Ed, 2009, 48: 9954
28. [28] Fang Q R, Makal T A, Young M D, Zhou H C. Comments Inorg Chem, 2010, 31: 165[28] Fang Q R, Makal T A, Young M D, Zhou H C. Comments Inorg Chem, 2010, 31: 165
29. [29] Xuan W M, Zhu C F, Liu Y, Cui Y. Chem Soc Rev, 2012, 41: 1677[29] Xuan W M, Zhu C F, Liu Y, Cui Y. Chem Soc Rev, 2012, 41: 1677
30. [30] Song L F, Zhang J, Sun L X, Xu F, Li F, Zhang H Z, Si X L, Jiao C L, Li Z B, Liu S, Liu Y L, Zhou H Y, Sun D L, Du Y, Cao Z, Gabelica Z. Energy Environ Sci, 2012, 5: 7508[30] Song L F, Zhang J, Sun L X, Xu F, Li F, Zhang H Z, Si X L, Jiao C L, Li Z B, Liu S, Liu Y L, Zhou H Y, Sun D L, Du Y, Cao Z, Gabelica Z. Energy Environ Sci, 2012, 5: 7508
31. [31] Qiu L G, Xu T, Li Z Q, Wang W, Wu Y, Jiang X, Tian X Y, Zhang L D. Angew Chem Int Ed, 2008, 47: 9487[31] Qiu L G, Xu T, Li Z Q, Wang W, Wu Y, Jiang X, Tian X Y, Zhang L D. Angew Chem Int Ed, 2008, 47: 9487
32. [32] Furukawa H, Nakamura T, Inagaki H, Nishikawa E, Imai C, Misono M. Chem Lett, 1988: 877[32] Furukawa H, Nakamura T, Inagaki H, Nishikawa E, Imai C, Misono M. Chem Lett, 1988: 877
33. [33] Furukawa H, Nishikawa E, Koyama T. JP Patent 62029546. 1987[33] Furukawa H, Nishikawa E, Koyama T. JP Patent 62029546. 1987
34. [34] Deng J F, Xu X H, Chen H Y, Jiang A R. Tetrahedron, 1992, 48: 3503[34] Deng J F, Xu X H, Chen H Y, Jiang A R. Tetrahedron, 1992, 48: 3503
35. [35] Schlichte K, Kratzke T, Kaskel S. Microporous Mesoporous Mater, 2004, 73: 81[35] Schlichte K, Kratzke T, Kaskel S. Microporous Mesoporous Mater, 2004, 73: 81
36. [36] Yuan D Q, Lu W G, Zhao D, Zhou H C. Adv Mater, 2011, 23: 3723[36] Yuan D Q, Lu W G, Zhao D, Zhou H C. Adv Mater, 2011, 23: 3723
37. [37] Chen H, Dai W L, Deng J F, Fan K N. Catal Lett, 2002, 81: 131[37] Chen H, Dai W L, Deng J F, Fan K N. Catal Lett, 2002, 81: 131
38. [38] Dai W L, Chen H, Cao Y, Li H X, Xie S H, Fan K N. Chem Commun, 2003: 892[38] Dai W L, Chen H, Cao Y, Li H X, Xie S H, Fan K N. Chem Commun, 2003: 892
39. [39] Gregg S J, Sing K S W. Adsorption, Surface Area and Porosity. London: Academic Press, 1997. 111[39] Gregg S J, Sing K S W. Adsorption, Surface Area and Porosity. London: Academic Press, 1997. 111
40. [40] Sun L B, Li J R, Park J, Zhou H C. J Am Chem Soc, 2012, 134: 126[40] Sun L B, Li J R, Park J, Zhou H C. J Am Chem Soc, 2012, 134: 126
41. [41] Wee L H, Wiktor C, Turner S, Vanderlinden W, Janssens N, Bajpe S R, Houthoofd K, Van Tendeloo G, De Feyter S, Kirschhock C E A, Martens J A. J Am Chem Soc, 2012, 134: 10911[41] Wee L H, Wiktor C, Turner S, Vanderlinden W, Janssens N, Bajpe S R, Houthoofd K, Van Tendeloo G, De Feyter S, Kirschhock C E A, Martens J A. J Am Chem Soc, 2012, 134: 10911
42. [42] Pauly T R, Liu Y, Pinnavaia T J, Billinge S J L, Rieker T P. J Am Chem Soc, 1999, 121: 8835[42] Pauly T R, Liu Y, Pinnavaia T J, Billinge S J L, Rieker T P. J Am Chem Soc, 1999, 121: 8835
43. [43] Férey G, Mellot-Draznieks C, Serre C, Millange F, Dutour J, Surblé S, Margiolaki I. Science, 2005, 309: 2040[43] Férey G, Mellot-Draznieks C, Serre C, Millange F, Dutour J, Surblé S, Margiolaki I. Science, 2005, 309: 2040
44. [44] Rao K M, Gobetto R, Iannibello A, Zecchina A. J Catal, 1989, 119: 512[44] Rao K M, Gobetto R, Iannibello A, Zecchina A. J Catal, 1989, 119: 512
45. [45] Damyanova S, Dimitrov L, Mariscal R, Fierro J L G, Petrov L, Sobrados I. Appl Catal A, 2003, 256: 183[45] Damyanova S, Dimitrov L, Mariscal R, Fierro J L G, Petrov L, Sobrados I. Appl Catal A, 2003, 256: 183
46. [46] Zang Y D, Shi J, Zhao X M, Kong L C, Zhang F M, Zhong Y J. Reac Kinet Mech Catal, 2013, 109: 77[46] Zang Y D, Shi J, Zhao X M, Kong L C, Zhang F M, Zhong Y J. Reac Kinet Mech Catal, 2013, 109: 77
47. [47] Wee L H, Bonino F, Lamberti C, Bordiga S, Martens J A. Green Chem, 2014, 16: 1351[47] Wee L H, Bonino F, Lamberti C, Bordiga S, Martens J A. Green Chem, 2014, 16: 1351
48. [48] Vimont A, Goupil J M, Lavalley J C, Daturi M, Surblé S, Serre C, Millange F, Férey G, Audebrand N. J Am Chem Soc, 2006, 128: 3218[48] Vimont A, Goupil J M, Lavalley J C, Daturi M, Surblé S, Serre C, Millange F, Férey G, Audebrand N. J Am Chem Soc, 2006, 128: 3218
49. [49] Youn M H, Kim H, Jung J C, Song I K, Barteau K P, Barteau M A. J Mol Catal A, 2005, 241: 227[49] Youn M H, Kim H, Jung J C, Song I K, Barteau K P, Barteau M A. J Mol Catal A, 2005, 241: 227
50. [50] Juan-Alcañiz J, Ramos-Fernandez E V, Lafont U, Gascon J, Kapteijn F. J Catal, 2010, 269: 229[50] Juan-Alcañiz J, Ramos-Fernandez E V, Lafont U, Gascon J, Kapteijn F. J Catal, 2010, 269: 229
51. [51] Duncan D C, Chambers R C, Hecht E, Hill C L. J Am Chem Soc, 1995, 117: 681[51] Duncan D C, Chambers R C, Hecht E, Hill C L. J Am Chem Soc, 1995, 117: 681
52. [52] Hu X F, Lu Y K, Dai F N, Liu C G, Liu Y Q. Microporous Mesoporous Mater, 2013, 170: 36[52] Hu X F, Lu Y K, Dai F N, Liu C G, Liu Y Q. Microporous Mesoporous Mater, 2013, 170: 36

扫一扫看文章

计量

PDF下载量: 0
文章访问数: 1756
HTML全文浏览量: 316

通讯作者: 陈斌, bchen63@163.com

1.
沈阳化工大学材料科学与工程学院沈阳 110142

一步法合成微-介孔多级孔道金属-有机骨架固载磷钨酸催化剂及其催化性能

English

One-pot synthesis of a hierarchical microporous-mesoporous phosphotungstic acid-HKUST-1 catalyst and its application in the selective oxidation of cyclopentene to glutaraldehyde

CCS Chemistry：嵌段共聚物自组装成 “三明治”二维有机材料，实现纳米级压力传感功能

CCS Chemistry：颜徐州、鲍哲南：你的皮肤可能是一片SPMs

CCS Chemistry：工作高效不疲劳，只须让催化剂动起来

CCS Chemistry：静电组装导向聚合- 聚电解质纳米凝胶量化制备新策略

CCS Chemistry：金黄色葡萄球菌醛基脱氢酶是如何识别特异性底物的？

计量

通讯作者: 陈斌, bchen63@163.com

中国化学会秘书处

一步法合成微-介孔多级孔道金属-有机骨架固载磷钨酸催化剂及其催化性能

English

One-pot synthesis of a hierarchical microporous-mesoporous phosphotungstic acid-HKUST-1 catalyst and its application in the selective oxidation of cyclopentene to glutaraldehyde

CCS Chemistry：嵌段共聚物自组装成 “三明治”二维有机材料，实现纳米级压力传感功能

CCS Chemistry：颜徐州、鲍哲南： 你的皮肤可能是一片SPMs

CCS Chemistry：工作高效不疲劳，只须让催化剂动起来

CCS Chemistry：静电组装导向聚合- 聚电解质纳米凝胶量化制备新策略

CCS Chemistry：金黄色葡萄球菌醛基脱氢酶是如何识别特异性底物的？

计量

文章相关

通讯作者: 陈斌, bchen63@163.com

中国化学会秘书处

CCS Chemistry：颜徐州、鲍哲南：你的皮肤可能是一片SPMs