Preparation,Structure and Characterization of Easily Peelable Nickel-Based Two-Dimensional Metal-Organic Frameworks

doi:10.12422/j.issn.1006-396X.2024.03.009

Abstract

Abstract:

The two-dimensional metal-organic framework nanosheets represent a novel class of two-dimensional materials, featuring a more exposed active site,rapid proton or electron transfer,and other advantages than bulk materials.It is a major challenge to prepare two-dimensional metal-organic framework crystalline materials that are easy to peel off into two-dimensional metal-organic nanosheets at present.In this paper,two novel nickel based two-dimensional metal organic framework crystalline materials Ni(C₉H₃O₆)(C₄H₆N₂)₂·0.6(C₂H₅OH)(1) and Ni₃(C₉H₃O₆)₃(C₅H₈N₂)₆·3.25(C₂H₅OH)(2),were prepared by a simple one-pot method using cheap and less toxic ethanol as the reaction medium,trimesic acid and N-imidazole as common ligands,and characterized and exfoliated.The reaction medium used in the experiment,ethanol,is less toxic, cheap, less polluting to the environment,and can be recycled,which meets the requirements of green chemistry.This shed light on the design and synthesis of crystalline peelable two-dimensional metal-organic framework crystal materials.

Key words: Two-dimensional metal-organic framework, Green synthesis, Material stripping

摘要：

二维金属-有机框架纳米片是一类新兴的二维材料，其与块体材料相比具有更多可暴露的活性位点、快速的质子或电子传递等优点。制备易剥离的二维金属-有机框架纳米片的前驱体，即二维金属-有机框架晶态材料是当前的一大挑战。以廉价且毒性较小的乙醇为反应介质、均苯三甲酸和N-基咪唑为共同配体，通过简单的一锅法制备了结构新颖的镍基二维金属-有机框架晶态材料Ni(C₉H₃O₆)(C₄H₆N₂)₂·0.6(C₂H₅OH)（1）和Ni₃(C₉H₃O₆)₃(C₅H₈N₂)₆·3.25(C₂H₅OH)（2），并对其进行了相关表征和剥离。实验中采用的反应介质乙醇毒性小、价格低廉、对环境污染性小且可循环利用，符合绿色化学的发展要求。该制备方法可为设计合成易剥离二维金属-有机框架晶态材料提供借鉴。

关键词: 二维金属-有机框架, 绿色合成, 材料剥离

CLC Number:

TQ426

Jie LIAN, Baokuan CHEN, Hongrui TIAN, Yafei GUO, Yanfeng BI. Preparation,Structure and Characterization of Easily Peelable Nickel-Based Two-Dimensional Metal-Organic Frameworks[J]. Journal of Petrochemical Universities, 2024, 37(3): 66-72.

廉洁, 陈宝宽, 田洪瑞, 郭亚飞, 毕研峰. 易剥离镍基二维金属-有机框架晶态材料的制备、结构及表征[J]. 石油化工高等学校学报, 2024, 37(3): 66-72.

Figures/Tables 9

References 24

1	ZHANG H，CHENG H M，YE P D.2D nanomaterials： Beyond graphene and transition metal dichalcogenides［J］.Chemical Society Reviews，2018，47（16）：6009-6012.
2	任翔宇，陈宝宽，孙京，等.双多酸基金属有机框架材料的合成及其光催化降解性能［J］.辽宁石油化工大学学报，2023，43（4）：51-58.
	REN X Y，CHEN B K，SUN J，et al.Double polyoxometalates-based metal-organic framework with photocatalytic degradation properties［J］.Journal of Liaoning Petrochemical University，2023，43（4）：51-58.
3	张倩，温月丽，王斌，等.层状金属氧化物用于二氧化碳吸附及其催化加氢转化的研究进展［J］.天然气化工（C1化学与化工），2021，46（3）：7-14.
	ZHANG Q，WEN Y L，WANG B，et al.Research progress of layered metal oxide in adsorption and catalytic hydrogenation of carbon dioxide［J］.Low-Carbon Chemistry and Chemical Engineering，2021，46（3）：7-14.
4	CHEN Z K，FAN Q Q，HUANG M H，et al.Synthesis of two-dimensional layered double hydroxide：A systematic overview［J］.CrystEngcomm，2022，24（26）：4639-4655.
5	孙彬，杨荣华，王俊杰，等.二维层状双金属氢氧化物的研究进展［J］.当代化工，2023，52（2）：415-427.
	SUN B，YANG R H，WANG J J，et al.Research progress of two-dimensional layered double hydroxide［J］.Contemporary Chemical Industry，2023，52（2）：415-427.
6	YIN X M，TANG C C，ZHENG Y，et al.Recent developments in 2D transition metal dichalcogenides：Phase transition and applications of the （quasi-） metallic phases［J］.Chemical Society Reviews，2021，50（18）：10087-10115.
7	郑宁来.层状多金属硫化物柴油脱硫催化剂国际领先［J］.石油炼制与化工，2016，47（9）：105.
	ZHENG N L.Layered polymetallic sulfide diesel desulfurization catalysts are internationally leading［J］.Petroleum Processing and Petrochemicals，2016，47（9）：105.
8	DENG X R，LIU H X，XU Y，et al.Designing highly stable ferrous selenide-black phosphorus nanosheets heteronanostructure via P-Se bond for MRI-guided photothermal therapy［J］.Journal of Nanobiotechnology，2021，19（1）：201.
9	PANDA P，SAMANTA R，BARMAN S.Facile synthesis of two-dimensional （2D） boron carbonitride and 2D porous boron carbonitride for excellent energy storage and gas adsorption applications［J］.Energy & Fuels，2023，37（7）：5540-5555.
10	袁瀚钦，董雯，吴兴良，等.改性石墨相氮化碳活化过硫酸盐降解水中有机污染物的研究进展［J］.化工环保，2022，42（6）：645-653.
	YUAN H Q，DONG W，WU X L，et al.Research progress of modified graphitic carbon nitride activating persulfate for degradation of organic pollutants in water［J］.Environmental Protection of Chemical Industry，2022，42（6）：645-653.
11	JIAO L，SEOW J Y R，SKINNER W S，et al.Metal–organic frameworks：Structures and functional applications［J］.Materials Today，2019，27：43-68.
12	UDOURIOH G A，SOLOMON M M，MATTHEWS-AMUNE C O，et al.Current trends in the synthesis，characterization and application of metal organic frameworks［J］.Reaction Chemistry & Engineering，2023，8（2）：278-310.
13	王海英，王程昊，张文成，等.MOF型Ca_0.7Nd_0.3CoO₃对木质素热解的催化性能研究［J］.石油化工高等学校学报，2022，35（5）：54-63.
	WANG H Y，WANG C H，ZHANG W C，et al.Study on the catalytic performance of metal-organic framework-type Ca_0.7Nd_0.3CoO₃ on pyrolysis of lignin［J］.Journal of Petrochemical Universities，2022，35（5）：54-63.
14	AFSHARIAZAR F，MORSALI A.Target-architecture engineering of a novel two-dimensional metal–organic framework for high catalytic performance［J］.Crystal Growth & Design，2019，19（8）：4239-4245.
15	TANG J，CAI M K，XIE G Q，et al.Amino‐induced 2D Cu‐based metal-organic framework as an efficient heterogeneous catalyst for aerobic oxidation of olefins［J］.Chemistry- A European Journal，2020，26（19）：4333-4340.
16	XUE Y P，ZHAO G C，YANG R Y，et al.2D metal-organic framework-based materials for electrocatalytic，photocatalytic and thermocatalytic applications［J］.Nanoscale，2021，13（7）：3911-3936.
17	朱敏，王艳芳，陈树军，等.M-MOF-74吸附分离天然气中CO₂的模拟研究［J］.辽宁石油化工大学学报，2019，39（3）：40-45.
	ZHU M，WANG Y F，CHEN S J，et al.Simulation study on the adsorption and separation of CO₂ from natural gas by M-MOF-74［J］.Journal of Liaoning Shihua University，2019，39（3）：40-45.
18	YANG S Q，ZHOU L，HE Y B，et al.Two-dimensional metal-organic framework with ultrahigh water stability for separation of acetylene from carbon dioxide and ethylene［J］.ACS Applied Materials & Interfaces，2022，14（29）：33429-33437.
19	MISHRA S，SINGH M K，PANDEY D，et al.A two-dimensional semiconducting Cu （Ⅰ）-MOF for binder and conductive additive-free supercapattery［J］.Journal of Materials Chemistry A，2024，12（8）：4534-4543.
20	陈雨，田欣雨，陈宁娜，等.碳布生长二维Ni-Mn MOF用于柔性超级电容器［J］.无机化学学报，2023，39（12）：2317-2327.
	CHEN Y，TIAN X Y，CHEN N N，et al.Two-dimensional Ni-Mn MOF grown on carbon cloth for flexible supercapacitors［J］.Chinese Journal of Inorganic Chemistry，2023，39（12）：2317-2327.
21	ZHU W J，YANG Y，JIN Q T，et al.Two-dimensional metal-organic-framework as a unique theranostic nano-platform for nuclear imaging and chemo-photodynamic cancer therapy［J］.Nano Research，2019，12（6）：1307-1312.
22	ZHANG M N，FAN T T，WANG Q S，et al.Zn/Cd/Cu- frameworks constructed by 3，3′-diphenyldicarboxylate and 1，4-bis （1，2，4-triazol-1-yl） butane：Syntheses，structure，luminescence and luminescence sensing for metal ion in aqueous medium［J］.Journal of Solid State Chemistry，2018，258：744-752.
23	BIENIEK A，WIŚNIEWSKI M，CZARNECKA J，et al.Porphyrin based 2D-MOF structures as dual-kinetic sorafenib nanocarriers for hepatoma treatment［J］.International Journal of Molecular Sciences，2021，22（20）：11161.
24	YANG W L，ZHANG X D，XIE Y.Advances and challenges in chemistry of two-dimensional nanosheets［J］.Nano Today，2016，11（6）：793-816.

参数	数值
参数	化合物1	化合物2
分子式	C_18.2H_18.6N₄NiO_6.6	C_63.5H_76.5N₁₂Ni₃O_21.25
相对分子质量	457.68	1 523.99
测试温度/K	273.0	273.0
波长/nm	0.071 073	0.071 070
晶系	三方	单斜
空间群	R-3 c	C2/c
a/nm	1.662 15（9）	2.898 30（2）
b/nm	1.662 15（9）	1.658 06(15)
c/nm	4.364 30（3）	1.560 94(15)
α/（º）	90	90
β/（º）	90	108
γ/（º）	120	90
体积/nm³	10.442 0(13)	7.112 6(11)
理论密度/(g·cm^-3)	181.310	41.369
吸收系数/mm^-1	0.88	0.86
收集/独立衍射数据	27 404/2 073（R_int=0.027）	49 865/6 287（R_int=0.04）
基于F²精修的吻合因子	1.058	1.039
可观察衍射的吻合因子	R₁=0.072，wR₂=0.229	R₁=0.049，wR₂=0.114

参数	数值
参数	化合物1	化合物2
分子式	C_18.2H_18.6N₄NiO_6.6	C_63.5H_76.5N₁₂Ni₃O_21.25
相对分子质量	457.68	1 523.99
测试温度/K	273.0	273.0
波长/nm	0.071 073	0.071 070
晶系	三方	单斜
空间群	R-3 c	C2/c
a/nm	1.662 15（9）	2.898 30（2）
b/nm	1.662 15（9）	1.658 06(15)
c/nm	4.364 30（3）	1.560 94(15)
α/（º）	90	90
β/（º）	90	108
γ/（º）	120	90
体积/nm³	10.442 0(13)	7.112 6(11)
理论密度/(g·cm^-3)	181.310	41.369
吸收系数/mm^-1	0.88	0.86
收集/独立衍射数据	27 404/2 073（R_int=0.027）	49 865/6 287（R_int=0.04）
基于F²精修的吻合因子	1.058	1.039
可观察衍射的吻合因子	R₁=0.072，wR₂=0.229	R₁=0.049，wR₂=0.114

[1]	Weijian TANG, Yujia WANG, Na SUN, Haiyan WANG. Research Progress of Catalysts for Cyclohexylbenzene Synthesis Based on Different Routes [J]. Journal of Petrochemical Universities, 2024, 37(3): 17-24.
[2]	Qijie XU, Honghao WANG, Lirong LÜ, Yaxin JIANG, Xiaoning HOU, Lei ZHANG, Zhixian GAO. Effect of Metal Loading on Catalytic CO⁃Prox Performance of CuO/NiO⁃CeO₂ [J]. Journal of Petrochemical Universities, 2024, 37(2): 42-49.
[3]	Changhe LÜ, Dianqing WU, Kaiwen ZHANG, Dongbei YU, Caishun ZHANG, Jiao HAN, Zhixian GAO. Characteristics of Methanol Steam Reforming Catalyzed by Cu⁃Mn⁃Al Ternary Spinel [J]. Journal of Petrochemical Universities, 2024, 37(2): 50-57.
[4]	Shengdi LI, Haicheng XIAO, Zhijie WU. Research Progress of Cobalt⁃Based Catalysts for Fischer⁃Tropsch Synthesis [J]. Journal of Petrochemical Universities, 2024, 37(1): 34-42.
[5]	Jingwei ZHANG, Yu HUI, Ye YANG, Qiang LI, Yucai QIN, Lijuan SONG, Shengwen LI. Controlled Synthesis of B⁃MFI Zeolite and Application for Butene Double Bond Isomerization [J]. Journal of Petrochemical Universities, 2023, 36(5): 31-37.
[6]	Xi Chen, Ying Jin, Ji Ma, Leilei Zhang, Zhaoyuan Song. Study on Cobalt Free Iron Base Like Perovskite as Cathode of SOFC [J]. Journal of Petrochemical Universities, 2023, 36(4): 69-74.
[7]	Shiao Gao, Zhijie Wu. Advances in the One⁃Dimensional Pore Zeolite for Hydroisomerization [J]. Journal of Petrochemical Universities, 2023, 36(2): 51-62.
[8]	Xinyu Yang, Shu Sun, Yan Shi, Xu Feng, Jiao Han, Caishun Zhang, Lei Zhang, Zhixian Gao. Effects of Hydrothermal Reaction Time on the Performance of CuO/CeO₂ Catalyst for Hydrogen Production from Steam Reforming Methanol [J]. Journal of Petrochemical Universities, 2023, 36(2): 63-69.
[9]	Lü Yu, Xiaoning Wang, Zhangxiong Wu. Research Progress in Synthesis of Cobalt⁃Based Catalysts and Peroxymonosulfate Activation [J]. Journal of Petrochemical Universities, 2022, 35(5): 12-24.
[10]	Jiangqian Yang, Meng Liu, Sida Ge, Zhijie Wu. Synthesis and Properties of Y Zeolite⁃Encapsulated Ru Metal Catalyst via Different Methods [J]. Journal of Petrochemical Universities, 2022, 35(5): 36-45.