卤素负载锌-腺嘌呤骨架材料的构建及无助剂催化CO2环加成反应

doi:10.11949/0438-1157.20210033

摘要/Abstract

摘要：

富氮型金属有机骨架材料（MOFs）具有良好的CO₂捕集性能，但其CO₂催化性能常需添加带氢键或亲核基团的助催化剂。以硝酸锌-腺嘌呤-异烟酸［Zn（NO₃）₂-Ad-Int-DMF］构建稳健的骨架材料，发现其催化合成碳酸丙烯酯（PC）收率不足2%；尝试选型锌盐前体引入亲核卤素，在DMF溶剂中部分卤代锌盐不能络合结晶成MOFs，而形成的ZnI₂-Ad-Int-DMF收率提升至19.5%；溶剂由DMF调变为H₂O-DMF混合溶剂，H₂O的引入避免了卤素对金属和配体间络合的影响，使得以ZnCl₂、ZnBr₂和ZnI₂为前体均能晶化成MOFs，其热分解起始温度（Tonset，434℃）明显高于ZnI₂-Ad-Int-DMF（280℃），而比表面积（<14 m²/g）明显小于后者（571 m²/g），造成活性低于后者。通过CO₂吸附脉冲和UV-Vis漫反射推测I^-由于与Zn碱位的相互作用而均匀吸附于骨架上。进而，在无助剂、无溶剂工况下对CO₂环加成反应进行活性评价。温度升高显著提升PC产率，140℃下ZnI₂-Ad-Int-DMF催化产率可达98.5%，但由于吸附在骨架上的卤素在高温、溶剂环境下会脱落，造成重复性实验中活性下降，而该类MOFs在反应前后骨架保持稳定，未造成坍塌或明显孔堵塞现象。后续如能强化卤素的吸附或温和化反应条件，则具有良好的应用潜力。

关键词: CO₂, 腺嘌呤, 金属有机骨架, 碳酸丙烯酯, 环氧丙烷

Abstract:

N-Rich metal organic framework materials (MOFs) have good CO₂ capture performance, but their CO₂ catalytic performance often requires the addition of co-catalysts with hydrogen bonds or nucleophilic groups. In this work, a stable Zn(NO₃)₂-Ad-Int-DMF (Ad=adenine, Int=isonicotinic acid) framework was constructed, and showed low activity (<2%) on propylene carbonate (PC) synthesis. Zinc halide precursors were selected to bring in nucleophilic halogen, only ZnI₂-Ad-Int-DMF was crystallized in DMF solvent, and its activity reached 19.5%. Then, the solvent was modulated from DMF to H₂O-DMFmixed solvent, MOFs could be constructed from all of ZnCl₂,ZnBr₂ and ZnI₂. After the introduction of H₂O, metal could be coordinated with organic ligands without halogen interference. These MOFs grown in H₂O-DMF showed an obviously higher initial decomposing temperature (Tonset, 434℃) and smaller BET (<14 m²/g) than the one in DMF (280℃,571 m²/g), consequently with lower activity. Then, it was speculated that iodine was adsorbed uniformly on alkaline Zn in the framework according to the CO₂pulse adsorption and UV-Vis diffuse reflectance spectra. The activity evaluation was tested on CO₂ cycloaddition under no cocatalyst and no solvent. The activity was promoted significantly with temperature increasing, the yield for ZnI₂-Ad-Int-DMF could reach 98.5% at 140℃. The halogen would fall from the framework under high temperature and solvent environment, which lead to the decrease of activity in the repeatability test. Nonetheless, the framework kept stable before and after reaction, no collapse and remarkable pore blocking were happened. If the halogen adsorption could be strengthened or reaction condition got milder, it would exhibit a good application potential.

Key words: CO₂, adenine, metal-organic frameworks, propylene carbonate, propylene oxide

中图分类号:

TQ 032.4

王结祥, 李洪国, 叶松寿, 郑进保, 陈秉辉. 卤素负载锌-腺嘌呤骨架材料的构建及无助剂催化CO₂环加成反应[J]. 化工学报, 2021, 72(7): 3686-3695.

WANG Jiexiang, LI Hongguo, YE Songshou, ZHENG Jinbao, CHEN Binghui. Halogen-rich zinc-adeninate framework construction and its catalytic performance on CO₂cycloaddition without cocatalyst[J]. CIESC Journal, 2021, 72(7): 3686-3695.

图/表 11

图1 骨架材料的构建及催化CO2环加成反应

Fig.1 The construction of the framework material and its catalysis on CO2 cycloaddition

图2 不同阴离子锌盐前体合成Zn-Ad-Int-DMF用于CO2环加成反应，其中NO3-+KI指Zn(NO3)2-Ad-Int-DMF中添加20%的KI[反应条件：PO 30 ml，PCO2 4 MPa（初始压力），催化剂 0.5 g，KI 0.1 g（如有添加），T=100℃，t=12 h]

Fig.2 Zn-Ad-Int-DMF prepared by different zinc salts and their catalytic activity comparison. Herein, NO3-+KI meant Zn(NO3)2-Ad-Int-DMF with KI (20% MOF dosage) added [Reaction conditions: PO 30 ml, initial PCO2 4 MPa, catalyst dosage 0.5 g, KI 0.1 g (if added), T=100℃, t=12 h]

图3 不同生长条件下ZnX2-Ad-Int在显微镜下的形态（a）、粉末XRD结构对比（b）及单晶XRD结构精修（c）

Fig.3 The morphology through microscope (a), structure comparison through PXRD for framework materials under different growth conditions (b) and X-ray single crystal refining for ZnI2-Ad-Int-DMF structure (c)

图4 ZnI2-Ad-Int-DMF低分辨率SEM图及相应的元素EDS图

Fig.4 Low-resolution scanning electron microscope image for ZnI2-Ad-Int-DMF and corresponding EDS elemental mapping images

图5 ZnX2-Ad-Int-DMF和ZnX2-Ad-Int-H2O (X=NO3-, Cl-, Br-, I-)孔结构测试

Fig.5 Pore parameters test for ZnX2-Ad-Int-DMF and ZnX2-Ad-Int-H2O

图6 ZnX2-Ad-Int-DMF(X=NO3-, I-)的CO2脉冲吸附与UV-Vis漫反射光谱差异

Fig.6 The difference for ZnX2-Ad-Int (X=NO3-, I-) in CO2 pulse adsorption and UV-Vis diffuse reflectance spectra

图7 ZnX2-Ad-Int及反应温度对CO2催化性能影响[反应条件：PO 30 ml，PCO2 4 MPa（初始压力），催化剂 0.5 g，t=24 h；TON/TOF计算过程视I离子为活性位点]

Fig.7 Catalytic activity comparison for different ZnX2-Ad-Int at different reaction temperature[Reaction conditions: PO 30 ml, initial PCO2 4 MPa, catalyst dosage 0.5g, t=24 h. In TON/TOF calculation process, I- was regarded as active site]

图8 两种ZnI2-Ad-Int的重复性实验，以及通过XRF测定重复性催化剂的碘含量变化[反应条件：PO 30 ml，PCO24 MPa（初始压力），催化剂 0.5 g，t=24 h，T=140℃]

Fig.8 Recycling test for two kinds of ZnI2-Ad-Int and iodine capacity test for recycling catalyst through XRF[Reaction conditions: PO 30 ml, initialPCO2 4 MPa, catalyst dosage 0.5 g, t=24 h，T=140℃]

图9 ZnI2-Ad-Int的骨架稳定性分析

Fig.9 The framework stability analysis for ZnI2-Ad-Int

表1 反应前后ZnI2-Ad-Int的元素分析

Table 1 Elemental analysis of ZnI2-Ad-Int

Sample	C/N ratio	Content/%（mass）
Sample	C/N ratio	N	C	H
ZnI₂-Ad-Int-H₂O	1.86	28.38	52.74	6.29
ZnI₂-Ad-Int-H₂O-reacted	2.06	25.84	53.08	5.88
ZnI₂-Ad-Int-DMF	1.63	24.93	40.66	4.84
ZnI₂-Ad-Int-DMF-reacted	1.82	23.61	42.97	4.01

图10 ZnX2-Ad-Int的构建及其对CO2从吸附到活化的转变过程示意图

Fig.10 Schematic illustration for the construction of ZnX2-Ad-Int and the transformation process from CO2 adsorption to activation

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卤素负载锌-腺嘌呤骨架材料的构建及无助剂催化CO₂环加成反应

Halogen-rich zinc-adeninate framework construction and its catalytic performance on CO₂cycloaddition without cocatalyst

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