Effect of Axial Coordination of Iron Porphyrin on Their Nanostructures and Photocatalytic Performance

Enough exposure of an active face is a key factor of nanocatalysis for sustainable energy conversion. Here, we exhibit the effect of axial coordination of organic metal complex molecules on the morphology evolution and photocatalytic hydrogen evolution (PHE) activity of organic nanocrystals (ONCs)....

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Published in:Crystal growth & design 2019-06, Vol.19 (6), p.3279-3287
Main Authors: Tian, Xuemin, Lin, Chensheng, Zhong, Zhou, Li, Xiaoxin, Xu, Xiao, Liu, Jingjing, Kang, Longtian, Chai, Guoliang, Yao, Jiannian
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container_end_page 3287
container_issue 6
container_start_page 3279
container_title Crystal growth & design
container_volume 19
creator Tian, Xuemin
Lin, Chensheng
Zhong, Zhou
Li, Xiaoxin
Xu, Xiao
Liu, Jingjing
Kang, Longtian
Chai, Guoliang
Yao, Jiannian
description Enough exposure of an active face is a key factor of nanocatalysis for sustainable energy conversion. Here, we exhibit the effect of axial coordination of organic metal complex molecules on the morphology evolution and photocatalytic hydrogen evolution (PHE) activity of organic nanocrystals (ONCs). The three series of iron porphyrin (FeTPPX, X = Cl, O, and OH) ONCs are controllably synthesized via the cetyltrimethylammonium bromide (CTAB)-assisted chemical reaction at different pH values. The uniform zero-dimensional FeTPPCl ONCs, ultrafine one-dimensional [FeTPP]2O ONCs with a diameter of ∼35 nm, and ultrathin two-dimensional FeTPPOH·H2O ONCs with the thickness of a crystal cell (
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Here, we exhibit the effect of axial coordination of organic metal complex molecules on the morphology evolution and photocatalytic hydrogen evolution (PHE) activity of organic nanocrystals (ONCs). The three series of iron porphyrin (FeTPPX, X = Cl, O, and OH) ONCs are controllably synthesized via the cetyltrimethylammonium bromide (CTAB)-assisted chemical reaction at different pH values. The uniform zero-dimensional FeTPPCl ONCs, ultrafine one-dimensional [FeTPP]2O ONCs with a diameter of ∼35 nm, and ultrathin two-dimensional FeTPPOH·H2O ONCs with the thickness of a crystal cell (&lt;1 nm) can be obtained by adjusting the concentration and volume of CTAB during the hydrolysis reaction of iron porphyrin perchlorate (FeTPP·ClO4). The mechanism of morphology evolution is carefully investigated, revealing the synergistic effect of the axial ligand of FeTPPX and CTAB on the exposure of the hydrophilic active face parallel to the porphyrin ring. Size-, shape-, and axial ligand-dependent photocatalysis can be clearly observed. Without using a cocatalyst, the FeTPPOH·H2O ultrathin nanoflakes display the highest PHE rate (∼0.75 mmol/h/g), followed by FeTPPCl octahedrons (∼0.48 mmol/h/g) and [FeTPP]2O ultrafine nanorods (∼0.20 mmol/h/g). 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title Effect of Axial Coordination of Iron Porphyrin on Their Nanostructures and Photocatalytic Performance
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