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Adsorbent–Adsorbate Interactions in the Oxidation of HMF Catalyzed by Ni-Based MOFs: A DRIFT and FT-IR Insight
The Journal of Physical Chemistry C ( IF 3.3 ) Pub Date : 2016-07-07 00:00:00 , DOI: 10.1021/acs.jpcc.6b05428
Carlo Lucarelli 1, 2 , Simona Galli 1, 2 , Angelo Maspero 1 , Alessandro Cimino 1 , Claudia Bandinelli 3 , Alice Lolli 3 , Juliana Velasquez Ochoa 3 , Angelo Vaccari 3 , Fabrizio Cavani 3 , Stefania Albonetti 3
The Journal of Physical Chemistry C ( IF 3.3 ) Pub Date : 2016-07-07 00:00:00 , DOI: 10.1021/acs.jpcc.6b05428
Carlo Lucarelli 1, 2 , Simona Galli 1, 2 , Angelo Maspero 1 , Alessandro Cimino 1 , Claudia Bandinelli 3 , Alice Lolli 3 , Juliana Velasquez Ochoa 3 , Angelo Vaccari 3 , Fabrizio Cavani 3 , Stefania Albonetti 3
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The three Ni-based metal–organic frameworks (MOFs) Ni(BDP), Ni(BPEB), and Ni3(BTP)2 [H2BDP = 1,4-(4-bispyrazolyl)benzene; H2BPEB = 1,4-bis(1H-pyrazol-4-ylethynyl)benzene; H3BTP = 1,3,5-tris(1H-pyrazol-4-yl)benzene], possessing square planar, potentially accessible metal sites, were preliminarily tested as catalysts in the base-free selective oxidation of hydroxymethylfurfural to 2,5-diformylfuran (DFF). While Ni(BDP) undergoes degradation, Ni3(BTP)2 is the most active of the three MOFs, yielding 27% DFF after 24 h with a selectivity close to 100% under relatively mild reaction conditions (120 °C, 30 bar O2, water as solvent). Upon flowing a model probe, in situ DRIFT and FT-IR spectroscopy were employed to rationalize the different performances of Ni(BPEB) and Ni3(BTP)2 in terms of adsorbate–adsorbent interactions: Not only hydrogen bonds are at work between the hydroxyl functionality of the probe and the pore walls of the MOF, but also and more importantly, bands ascribed to Ni-OR stretching are detected, denouncing the insurgence of Ni-probe interactions. The different intensity of these bands in the two cases confirms the different accessibility of the metal centers, as suggested by crystal structure analysis and catalytic tests.
中文翻译：
镍基MOF催化HMF氧化中的吸附剂-吸附剂相互作用：DRIFT和FT-IR洞察
三个基于镍的金属有机骨架（MOF）Ni（BDP），Ni（BPEB）和Ni 3（BTP）2 [H 2 BDP = 1,4-（4-双吡唑基）苯；H 2 BPEB = 1,4-双（1 H-吡唑-4-基乙炔基）苯; 初步测试了H 3 BTP = 1,3,5-三（1 H-吡唑-4-基）苯具有方形平面，可能易接近的金属位点，作为催化剂在羟甲基糠醛的无碱选择性氧化中反应成2， 5-二甲酰呋喃（DFF）。Ni（BDP）发生降解时，Ni 3（BTP）2是三种MOF中活性最高的，在相对温和的反应条件下（120°C，30 bar O），在24 h后产生的DFF为27％，选择性接近100％。2，以水为溶剂）。在流过模型探针后，采用原位DRIFT和FT-IR光谱法合理化了Ni（BPEB）和Ni 3（BTP）2在吸附物-吸附剂相互作用方面的不同性能：不仅氢键在两个键之间起作用检测到探针的羟基官能团和MOF的孔壁，而且更重要的是，检测到归因于Ni-OR拉伸的条带，这表明Ni-探针相互作用势在必行。如晶体结构分析和催化测试所示，在两种情况下，这些谱带的强度不同证实了金属中心的可及性不同。
更新日期：2016-07-07
中文翻译：
镍基MOF催化HMF氧化中的吸附剂-吸附剂相互作用：DRIFT和FT-IR洞察
三个基于镍的金属有机骨架（MOF）Ni（BDP），Ni（BPEB）和Ni 3（BTP）2 [H 2 BDP = 1,4-（4-双吡唑基）苯；H 2 BPEB = 1,4-双（1 H-吡唑-4-基乙炔基）苯; 初步测试了H 3 BTP = 1,3,5-三（1 H-吡唑-4-基）苯具有方形平面，可能易接近的金属位点，作为催化剂在羟甲基糠醛的无碱选择性氧化中反应成2， 5-二甲酰呋喃（DFF）。Ni（BDP）发生降解时，Ni 3（BTP）2是三种MOF中活性最高的，在相对温和的反应条件下（120°C，30 bar O），在24 h后产生的DFF为27％，选择性接近100％。2，以水为溶剂）。在流过模型探针后，采用原位DRIFT和FT-IR光谱法合理化了Ni（BPEB）和Ni 3（BTP）2在吸附物-吸附剂相互作用方面的不同性能：不仅氢键在两个键之间起作用检测到探针的羟基官能团和MOF的孔壁，而且更重要的是，检测到归因于Ni-OR拉伸的条带，这表明Ni-探针相互作用势在必行。如晶体结构分析和催化测试所示，在两种情况下，这些谱带的强度不同证实了金属中心的可及性不同。
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