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Entrapped Molecular Photocatalyst and Photosensitizer in Metal–Organic Framework Nanoreactors for Enhanced Solar CO2 Reduction
ACS Catalysis ( IF 11.3 ) Pub Date : 2021-01-05 , DOI: 10.1021/acscatal.0c04673 Philip M. Stanley 1, 2 , Christopher Thomas 2 , Erling Thyrhaug 3 , Alexander Urstoeger 4 , Michael Schuster 4 , Jürgen Hauer 3 , Bernhard Rieger 2 , Julien Warnan 1 , Roland A. Fischer 1
ACS Catalysis ( IF 11.3 ) Pub Date : 2021-01-05 , DOI: 10.1021/acscatal.0c04673 Philip M. Stanley 1, 2 , Christopher Thomas 2 , Erling Thyrhaug 3 , Alexander Urstoeger 4 , Michael Schuster 4 , Jürgen Hauer 3 , Bernhard Rieger 2 , Julien Warnan 1 , Roland A. Fischer 1
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Herein, we report on a molecular catalyst embedding metal–organic framework (MOF) that enables enhanced photocatalytic CO2 reduction activity. A benchmark photocatalyst fac-ReBr(CO)3(4,4′-dcbpy) (dcbpy = dicarboxy-2,2′-bipyridine) and photosensitizer Ru(bpy)2(5,5′-dcbpy)Cl2 (bpy = 2,2′-bipyridine) were synergistically entrapped inside the cages of the nontoxic and inexpensive MIL-101-NH2(Al) through noncovalent host–guest interactions. The heterogeneous material improved Re catalyst stabilization under photocatalytic CO2 reduction conditions as selective CO evolution was prolonged from 1.5 to 40 h compared to the MOF-free photosystem upon reactivation with additional photosensitizer. By varying ratios of immobilized catalyst to photosensitizer, we demonstrated and evaluated the effect of reaction environment modulation in defined MOF cages acting as a nanoreactor. This illustrated the optimal efficiency for two photosensitizers and one catalyst per cage and further led to the determination of ad hoc relationships between molecular complex size, MOF pore windows, and number of hostable molecules per cage. Differing from typical homogeneous systems, photosensitizer—and not catalyst—degradation was identified as a major performance-limiting factor, providing a future route to higher turnover numbers via a rational choice of parameters.
中文翻译：
金属-有机骨架纳米反应器中捕获的分子光催化剂和光敏剂可增强太阳能CO 2还原
在此，我们报道了一种嵌入金属-有机骨架（MOF）的分子催化剂，该分子能够增强光催化的CO 2还原活性。基准光催化剂fac -ReBr（CO）3（4,4'-dcbpy）（dcbpy =二羧基-2,2'-联吡啶）和光敏剂Ru（bpy）2（5,5'-dcbpy）Cl 2（bpy =通过非共价的宿主-客体相互作用，将2,2'-联吡啶）协同捕获在无毒且廉价的MIL-101-NH 2（Al）的笼子中。非均相材料改善了光催化CO 2下Re催化剂的稳定性与无MOF的光系统经额外的光敏剂重新活化相比，选择性CO释放的还原条件可延长1.5至40小时。通过改变固定化催化剂与光敏剂的比例，我们证明并评估了在定义的充当纳米反应器的MOF笼中反应环境调节的效果。这说明了每个笼子中两种光敏剂和一种催化剂的最佳效率，并进一步确定了分子复合物大小，MOF孔窗和每个笼子中可容纳的分子数之间的特殊关系。与典型的均相系统不同，光敏剂而不是催化剂的降解被认为是主要的性能限制因素，它通过合理选择参数为将来获得更高的营业额提供了途径。
更新日期：2021-01-15
中文翻译：
金属-有机骨架纳米反应器中捕获的分子光催化剂和光敏剂可增强太阳能CO 2还原
在此，我们报道了一种嵌入金属-有机骨架（MOF）的分子催化剂，该分子能够增强光催化的CO 2还原活性。基准光催化剂fac -ReBr（CO）3（4,4'-dcbpy）（dcbpy =二羧基-2,2'-联吡啶）和光敏剂Ru（bpy）2（5,5'-dcbpy）Cl 2（bpy =通过非共价的宿主-客体相互作用，将2,2'-联吡啶）协同捕获在无毒且廉价的MIL-101-NH 2（Al）的笼子中。非均相材料改善了光催化CO 2下Re催化剂的稳定性与无MOF的光系统经额外的光敏剂重新活化相比，选择性CO释放的还原条件可延长1.5至40小时。通过改变固定化催化剂与光敏剂的比例，我们证明并评估了在定义的充当纳米反应器的MOF笼中反应环境调节的效果。这说明了每个笼子中两种光敏剂和一种催化剂的最佳效率，并进一步确定了分子复合物大小，MOF孔窗和每个笼子中可容纳的分子数之间的特殊关系。与典型的均相系统不同，光敏剂而不是催化剂的降解被认为是主要的性能限制因素，它通过合理选择参数为将来获得更高的营业额提供了途径。
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