The growth process of metal-organic framework (MOF) nanocrystals defines their properties and functions. However, defects may be prevalent during the crystallization of even seemingly perfect MOFs, such as zeolitic imidazolate framework-8 (ZIF-8), and yet direct probing of such structural defects has been challenging because of the lack of nanoscale techniques to locally examine individual nanocrystals. Here, we directly study local defects, such as missing linkers or metal vacancies, in ZIF-8 nano- and microcrystals with near-field IR nanospectroscopy combined with density functional theory calculations. We track the chemical changes during crystallization and show that structural defects like zinc cations that are bound to molecules of the reactant gradually disappear with ripening of the crystals, while dangling and missing linker defects prevail. The resulting defect-terminating groups or open-metal sites produce mechanical anisotropy and reduce the Young's modulus, as measured via tip force microscopy with nanoscale resolution and supported by theoretical modeling. However, these structural defects also open the door for defect engineering to tune the performance of ZIF-8 by offering additional adsorption sites for targeted catalytic reactions, chemical sensing, or gas capture.
机构:
Nanjing Normal Univ, Sch Chem & Mat Sci, Nanjing 210046, Jiangsu, Peoples R ChinaNanjing Normal Univ, Sch Chem & Mat Sci, Nanjing 210046, Jiangsu, Peoples R China
机构:
Nankai Univ, Coll Chem, Res Ctr Analyt Sci, State Key Lab Med Chem Biol, Tianjin 300071, Peoples R ChinaNankai Univ, Coll Chem, Res Ctr Analyt Sci, State Key Lab Med Chem Biol, Tianjin 300071, Peoples R China
Fu Yanyan
Yan Xiuping
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Nankai Univ, Coll Chem, Res Ctr Analyt Sci, State Key Lab Med Chem Biol, Tianjin 300071, Peoples R ChinaNankai Univ, Coll Chem, Res Ctr Analyt Sci, State Key Lab Med Chem Biol, Tianjin 300071, Peoples R China
机构:
Zhejiang Sci Tech Univ, Sch Mat Sci & Engn, Hangzhou 310018, Peoples R ChinaZhejiang Sci Tech Univ, Sch Mat Sci & Engn, Hangzhou 310018, Peoples R China
Ma, Jiaqi
Fan, Linkun
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Zhejiang Sci Tech Univ, Sch Mat Sci & Engn, Hangzhou 310018, Peoples R ChinaZhejiang Sci Tech Univ, Sch Mat Sci & Engn, Hangzhou 310018, Peoples R China
Fan, Linkun
Wang, Xusheng
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机构:
Zhejiang Sci Tech Univ, Sch Mat Sci & Engn, Hangzhou 310018, Peoples R China
Zhejiang Sci Tech Univ, Shengzhou Innovat Res Inst, Shengzhou 312400, Zhejiang, Peoples R China
Jinan Univ, Guangdong Prov Key Lab Funct Supramol Coordinat Ma, Guangzhou 510632, Peoples R ChinaZhejiang Sci Tech Univ, Sch Mat Sci & Engn, Hangzhou 310018, Peoples R China
Wang, Xusheng
Li, Lan
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机构:
China Jiliang Univ, Coll Mat & Chem, Hangzhou 310018, Peoples R ChinaZhejiang Sci Tech Univ, Sch Mat Sci & Engn, Hangzhou 310018, Peoples R China
Li, Lan
Zhang, Yiming
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机构:
Lanzhou Univ Technol, Sch Mat Sci & Engn, Lanzhou 730050, Peoples R ChinaZhejiang Sci Tech Univ, Sch Mat Sci & Engn, Hangzhou 310018, Peoples R China
Zhang, Yiming
Zhao, Guixia
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机构:
North China Elect Power Univ, Coll Environm Sci & Engn, Beijing 102206, Peoples R ChinaZhejiang Sci Tech Univ, Sch Mat Sci & Engn, Hangzhou 310018, Peoples R China
Zhao, Guixia
Chai, Bo
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机构:
Wuhan Polytech Univ, Sch Chem & Environm Engn, Wuhan 430023, Peoples R ChinaZhejiang Sci Tech Univ, Sch Mat Sci & Engn, Hangzhou 310018, Peoples R China
Chai, Bo
Gao, Junkuo
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机构:
Zhejiang Sci Tech Univ, Sch Mat Sci & Engn, Hangzhou 310018, Peoples R ChinaZhejiang Sci Tech Univ, Sch Mat Sci & Engn, Hangzhou 310018, Peoples R China
机构:
Nanjing Normal Univ, Sch Chem & Mat Sci, Nanjing 210046, Jiangsu, Peoples R ChinaNanjing Normal Univ, Sch Chem & Mat Sci, Nanjing 210046, Jiangsu, Peoples R China
机构:
Nankai Univ, Coll Chem, Res Ctr Analyt Sci, State Key Lab Med Chem Biol, Tianjin 300071, Peoples R ChinaNankai Univ, Coll Chem, Res Ctr Analyt Sci, State Key Lab Med Chem Biol, Tianjin 300071, Peoples R China
Fu Yanyan
Yan Xiuping
论文数: 0引用数: 0
h-index: 0
机构:
Nankai Univ, Coll Chem, Res Ctr Analyt Sci, State Key Lab Med Chem Biol, Tianjin 300071, Peoples R ChinaNankai Univ, Coll Chem, Res Ctr Analyt Sci, State Key Lab Med Chem Biol, Tianjin 300071, Peoples R China
机构:
Zhejiang Sci Tech Univ, Sch Mat Sci & Engn, Hangzhou 310018, Peoples R ChinaZhejiang Sci Tech Univ, Sch Mat Sci & Engn, Hangzhou 310018, Peoples R China
Ma, Jiaqi
Fan, Linkun
论文数: 0引用数: 0
h-index: 0
机构:
Zhejiang Sci Tech Univ, Sch Mat Sci & Engn, Hangzhou 310018, Peoples R ChinaZhejiang Sci Tech Univ, Sch Mat Sci & Engn, Hangzhou 310018, Peoples R China
Fan, Linkun
Wang, Xusheng
论文数: 0引用数: 0
h-index: 0
机构:
Zhejiang Sci Tech Univ, Sch Mat Sci & Engn, Hangzhou 310018, Peoples R China
Zhejiang Sci Tech Univ, Shengzhou Innovat Res Inst, Shengzhou 312400, Zhejiang, Peoples R China
Jinan Univ, Guangdong Prov Key Lab Funct Supramol Coordinat Ma, Guangzhou 510632, Peoples R ChinaZhejiang Sci Tech Univ, Sch Mat Sci & Engn, Hangzhou 310018, Peoples R China
Wang, Xusheng
Li, Lan
论文数: 0引用数: 0
h-index: 0
机构:
China Jiliang Univ, Coll Mat & Chem, Hangzhou 310018, Peoples R ChinaZhejiang Sci Tech Univ, Sch Mat Sci & Engn, Hangzhou 310018, Peoples R China
Li, Lan
Zhang, Yiming
论文数: 0引用数: 0
h-index: 0
机构:
Lanzhou Univ Technol, Sch Mat Sci & Engn, Lanzhou 730050, Peoples R ChinaZhejiang Sci Tech Univ, Sch Mat Sci & Engn, Hangzhou 310018, Peoples R China
Zhang, Yiming
Zhao, Guixia
论文数: 0引用数: 0
h-index: 0
机构:
North China Elect Power Univ, Coll Environm Sci & Engn, Beijing 102206, Peoples R ChinaZhejiang Sci Tech Univ, Sch Mat Sci & Engn, Hangzhou 310018, Peoples R China
Zhao, Guixia
Chai, Bo
论文数: 0引用数: 0
h-index: 0
机构:
Wuhan Polytech Univ, Sch Chem & Environm Engn, Wuhan 430023, Peoples R ChinaZhejiang Sci Tech Univ, Sch Mat Sci & Engn, Hangzhou 310018, Peoples R China
Chai, Bo
Gao, Junkuo
论文数: 0引用数: 0
h-index: 0
机构:
Zhejiang Sci Tech Univ, Sch Mat Sci & Engn, Hangzhou 310018, Peoples R ChinaZhejiang Sci Tech Univ, Sch Mat Sci & Engn, Hangzhou 310018, Peoples R China