General Strategy for In situ Synthesis of NENU-n Series Polyoxometalate-based MOFs on Copper Foil

doi:10.7503/cjcu20210557

Abstract

Abstract:

The NENU-n series polyoxometalate-based metal-organic framework（POM@MOFs） are formed by encapsulating a series of excellent Keggin type polyoxometalates into Cu₃（BTC）₂ framework， showing excellent performance in the fields of catalysis and proton conduction. In this work， a new method of in situ synthesis of POM@MOFs on copper foil was developed on the basis of the previous work， that is， oxygen was added into the reaction solution， and the oxygen could oxidize Cu⁰ to Cu²⁺ under acidic conditions to provide copper ion source for the growth of the metal-organic framework. Thus， even though the oxidation capacity of Keggin tungsten polyoxometalates is weak， pure phase products of NENU-n series hybrids can also be synthesized in situ on copper substrates. The method is simple， rapid and high atomic economy at room temperature. Moreover， we found that POM@MOFs with controllable morphology can be generated by using this method without adding any regulator， and its morphology depends on the charge of heteropoly acid anions. The heteropoly anion with high charge can obtain the cubic morphology， while the heteropoly anion with low charge can obtain the octahedral shape. Catalytic oxidation of simulated mustard gas （2-chloroethylethyl sulfide， CEES） was studied by using the synthesized materials. The results showed that the NENU-40［K₅BW₁₂O₄₀/Cu₃（BTC）₂］ with cubic morphology exposed more active sites and showed a better catalytic activity. CEES can be completely converted to non-toxic CEESO within 10 min.

Key words: Keggin type polyoxometalate, Metal-organic framework, Copper foil, In situ synthesis

CLC Number:

O611.4

TrendMD:

WANG Jie, HUO Haiyan, WANG Yang, ZHANG Zhong, LIU Shuxia. General Strategy for In situ Synthesis of NENU-n Series Polyoxometalate-based MOFs on Copper Foil[J]. Chem. J. Chinese Universities, 2022, 43(1): 20210557.

Figures/Tables 10

Fig.1 Surface structure of {111} facets with closed triangle H3BTC walls(A) and the surface structure of {100} facets with open square windows(B) in NENU?n

Table 1 Redox potentials of Keggin type POMs, Cu and O2 in aqueous solution[18]

Redox system	E ^0—/V	Redox system	E ^0—/V
PV^Ⅴ₂Mo₁₀O₄⁵₀^-/PV₂^ⅣMo₁₀O₄⁷₀^-	0.71	SiW₁^Ⅵ₂O₄⁴₀^-/SiW₁^Ⅵ₁W^ⅤO₄⁵₀^-	-0.15
PMo₁^Ⅵ₂O₄³₀^-/PMo₉^ⅥMo₃^ⅤO₄⁶₀^-	0.65	BW₁^Ⅵ₂O₄⁵₀^-/BW₁^Ⅵ₁W^ⅤO₄⁶₀^-	-0.36
Cu²⁺/Cu	0.34	O₂/H₂O	1.229
PW₁^Ⅵ₂O₄³₀^-/PW₁^Ⅵ₁W^ⅤO₄⁴₀^-	0.15

Fig.2 FTIR spectra(A) and PXRD patterns(B) of NENU?n encapsulating Keggin type POMs with different negative charges

Fig.3 SEM image(A) and corresponding elemental mappings of NENU?1(B―F)(B) C; (C) O; (D) Si; (E) Cu; (F) W.

Fig.4 SEM image(A) and corresponding elemental mappings of NENU?3(B―F)(B) C; (C) O; (D) Cu; (E) P; (F) W.

Fig.5 SEM image(A) and corresponding elemental mappings of NENU?40(B―F)(B) B; (C) C; (D) O; (E) Cu; (F) W.

Fig.6 SEM images of the as?synthesized NENU?3(A), NENU?1(B) and NENU?40(C) on Cu foil

Table 2 Catalytic oxidation of CEES under different catalytic conditions*

Entry	Catalyst	Molar ratio of CEES to H₂O₂	Time/min	Conversion（%）	Selectivity（%）
1	None	1∶1.5	180	―	―
2	H₃PW₁₂O₄₀	1∶1.5	180	99	100
3	H₄SiW₁₂O₄₀	1∶1.5	180	98	100
4	K₅BW₁₂O₄₀	1∶1.5	180	99	100
5	Cu₃（BTC）₂	1∶1.5	30	56.8	89
6	NENU?3	1∶1.5	30	100	100
7	NENU?3	1∶1	30	85.6	100
8	NENU?3	1∶5	30	100	100
9	NENU?1	1∶1.5	30	100	100
10	NENU?40	1∶1.5	10	100	100

Fig.7 General reaction pathways for CEES oxidation with hydrogen peroxide(A) and time profile for CEES oxidation using K5BW12O40, Cu3(BTC)2, NENU?40 and NENU?3 as catalysts(B)

Fig.8 Recycling test of NENU?40(A) and PXRD patterns of NENU?40 before recycling and after recycling for 5 times(B)

References 26

1	Yue Q.， Lu Y.， Zhang Z.， Tian H.， Wang H.， Li X.， Liu S.， New. J. Chem.， 2020， 44（39）， 16913―16920
2	Lai X.， Liu Y.， Yang G.， Liu S.， Shi Z.， Lu Y.， Luo F.， Liu S.， J. Mater. Chem. A.， 2017， 5（20）， 9611―9617
3	Liu Y.， Yang X.， Miao J.， Tang Q.， Liu S.， Shi Z.， Liu S.， Chem. Commun.（Camb）， 2014， 50（70）， 10023―10026
4	Wang S. S.， Yang G. Y.， Chem. Rev.， 2015， 115（11）， 4893―4962
5	Kozhevnikov I. V.， Chem. Rev.， 1998， 98（1）， 171―198
6	Peng Y. L.， Liu J.， Zhang H. F.， Luo D.， Li D.， Inorg. Chem. Front.， 2018， 5（7）， 1563―1569
7	Samaniyan M.， Mirzaei M.， Khajavian R.， Eshtiagh⁃Hosseini H.， Streb C.， ACS Catal.， 2019， 9（11）， 10174―10191
8	Song J.， Luo Z.， Britt D. K.， Furukawa H.， Yaghi O. M.， Hardcastle K. I.， Hill C. L.， J. Am. Chem. Soc.， 2011， 133（42）， 16839―16846
9	Sun C. Y.， Liu S. X.， Liang D. D.， Shao K. Z.， Ren Y. H.， Su Z. M.， J. Am. Chem. Soc.， 2009， 131（5）， 1883―1888
10	Liang D. D.， Liu S. X.， Ma F. J.， Wei F.， Chen Y. G.， Adv. Synth. Catal.， 2011， 353（5）， 733―742
11	Zhong X.， Lu Y.， Luo F.， Liu Y.， Li X.， Liu S.， Chemistry， 2018， 24（12）， 3045―3051
12	Liu Y. W.， Liu S. M.， Liu S. X.， Liang D. D.， Li S. J.， Tang Q.， Wang X. Q.， Miao J.， Shi Z.， Zheng Z. P.， Chemcatchem， 2013， 5（10）， 3086―3091
13	Liu Y.， Liu S.， He D.， Li N.， Ji Y.， Zheng Z.， Luo F.， Liu S.， Shi Z.， Hu C.， J. Am. Chem. Soc.， 2015， 137（39）， 12697―12703
14	Li X. H.， Liu Y. W.， Liu S. M.， Wang S.， Xu L.， Zhang Z.， Luo F.， Lu Y.， Liu S. X.， J. Mater. Chem. A， 2018， 6（11）， 4678―4685
15	Zhang Z.， Tao Y.， Tian H.， Yue Q.， Liu S.， Liu Y.， Li X.， Lu Y.， Sun Z.， Kraka E.， Liu S.， Chem. Mater.， 2020， 32（13）， 5550―5557
16	Li X. H.， Liu Y. W.， Lu Y.， Zhang Z.， Tian H. R.， Liu S. M.， Liu S. X.， Chem. Commun.（Camb）， 2020， 56（11）， 1641―1644
17	Deltcheff C. R， Fournier M.， Franck R.， Thouvenot R.， Inorg. Chem.， 1983， 22（2）， 207―216
18	Kozhevnikov I. V.， Russ. Chem. Rev.， 1987， 56（9）， 811―825
19	Tian H. R.， Zhang Z.， Liu S. M.， Dang T. Y.， Li X. H.， Lu Y.， Liu S. X.， J. Mater. Chem. A， 2020， 8（25）， 12398―12405
20	Buru C. T.， Li P.， Mehdi B. L.， Dohnalkova A.， Platero⁃Prats A. E.， Browning N. D.， Chapman K. W.， Hupp J. T.， Farha O. K.， Chem. Mater.， 2017， 29（12）， 5174―5181
21	Buru C. T.， Platero⁃Prats A. E.， Chica D. G.， Kanatzidis M. G.， Chapman K. W.， Farha O. K.， J. Mater. Chem. A， 2018， 6（17）， 7389―7394
22	Duncan D. C.， Chambers R. C.， Hecht E.， Hill C. L.， J. Am. Chem. Soc.， 2002， 117（2）， 681―691
23	Liu Q.， Jin L. N.， Sun W. Y.， Chem. Commun.（Camb）， 2012， 48（70）， 8814―8816
24	Liu Q.， Yang J. M.， Jin L. N.， Sun W. Y.， CrystEngComm， 2016， 18（22）， 4127―4132
25	Liu Y.， Zhang Y.， Chen J.， Pang H.， Nanoscale， 2014， 6（19）， 10989―10994
26	Umemura A.， Diring S.， Furukawa S.， Uehara H.， Tsuruoka T.， Kitagawa S.， J. Am. Chem. Soc.， 2011， 133（39）， 15506―15513

[1]	ZHAO Yingzhe, ZHANG Jianling. Applications of Metal-organic Framework-based Material in Carbon Dioxide Photocatalytic Conversion [J]. Chem. J. Chinese Universities, 2022, 43(7): 20220223.
[2]	LU Cong, LI Zhenhua, LIU Jinlu, HUA Jia, LI Guanghua, SHI Zhan, FENG Shouhua. Synthesis， Structure and Fluorescence Detection Properties of a New Lanthanide Metal-Organic Framework Material [J]. Chem. J. Chinese Universities, 2022, 43(6): 20220037.
[3]	TIAN Xueqin, MO Zheng, DING Xin, WU Pengyan, WANG Yu, WANG Jian. A Squaramide-containing Luminescent Metal-organic Framework as a High Selective Sensor for Histidine [J]. Chem. J. Chinese Universities, 2022, 43(2): 20210589.
[4]	XING Peiqi, LU Tong, LI Guanghua, WANG Liyan. Controllable Syntheses of Two Cd（II） Metal-organic Frameworks Possessing Related Structures [J]. Chem. J. Chinese Universities, 2022, 43(10): 20220218.
[5]	LI Shurong, WANG Lin, CHEN Yuzhen, JIANG Hailong. Research Progress of Metal⁃organic Frameworks on Liquid Phase Catalytic Chemical Hydrogen Production [J]. Chem. J. Chinese Universities, 2022, 43(1): 20210575.
[6]	ZHANG Chi, SUN Fuxing, ZHU Guangshan. Synthesis， N₂ Adsorption and Mixed-matrix Membrane Performance of Bimetal Isostructural CAU-21 [J]. Chem. J. Chinese Universities, 2022, 43(1): 20210578.
[7]	MO Zongwen, ZHANG Xuewen, ZHOU Haolong, ZHOU Dongdong, ZHANG Jiepeng. Guest-responses of A Porous Coordination Polymer Based on Synergistic Hydrogen Bonds [J]. Chem. J. Chinese Universities, 2022, 43(1): 20210576.
[8]	SHI Xiaofan, ZHU Jian, BAI Tianyu, FU Zixuan, ZHANG Jijie, BU Xianhe. Research Status and Progress of MOFs with Application in Photoelectrochemical Water-splitting [J]. Chem. J. Chinese Universities, 2022, 43(1): 20210613.
[9]	WU Ji, ZHANG Hao, LUO Yuhui, GENG Wuyue, LAN Yaqian. A Microporous Cationic Ga（III）-MOF with Fluorescence Properties for Selective sensing Fe³⁺ Ion and Nitroaromatic Compounds [J]. Chem. J. Chinese Universities, 2022, 43(1): 20210617.
[10]	LI Wen, QIAO Junyi, LIU Xinyao, LIU Yunling. Zirconium-based Metal-Organic Framework with Naphthalene for Fluorescent Detection of Nitroaromatic Explosives in Water [J]. Chem. J. Chinese Universities, 2022, 43(1): 20210654.
[11]	LIU Xueguang, YANG Xiaoshan, MA Jingjing, LIU Weisheng. Separating Methyl Blue Selectively from the Mixture of Dyes by Europium Metal-organic Frameworks [J]. Chem. J. Chinese Universities, 2022, 43(1): 20210715.
[12]	HAN Zongsu, YU Xiaoyong, MIN Hui, SHI Wei, CHENG Peng. A Rare Earth Metal-Organic Framework with H₆TTAB Ligand [J]. Chem. J. Chinese Universities, 2022, 43(1): 20210342.
[13]	ZHANG Renli, WANG Yao, YU Zhiquan, SUN Zhichao, WANG Anjie, LIU Yingya. Molybdenum Peroxide Anchored on Fluoronated UiO-66 as Catalyst in the Oxidation of Sulfur Containing Compounds [J]. Chem. J. Chinese Universities, 2021, 42(6): 1914.
[14]	ZHAO Yangyang, LIU Qiyong, CHEN Boxin, ZHAO Bin, ZHOU Haimei, LI Xinxin, ZHENG Dan, FENG Fei. Silicon-based Micro Gas Chromatographic Column Using Metal-Organic Framework Material ZIF-8 as Stationary Phase [J]. Chem. J. Chinese Universities, 2021, 42(6): 1736.
[15]	WANG Longjie, FAN Hongchuan, QIN Yu, CAO Qiue, ZHENG Liyan. Research Progress of Metal-organic Frameworks in the Field of Chemical Separation and Analysis [J]. Chem. J. Chinese Universities, 2021, 42(4): 1167.