MOF‐Based Heterojunctions: The Effect of Materials Architecture in TiO<sub>2</sub>/MOF Composites on CO<sub>2</sub> Photoreduction and Charge Transfer (Small 11/2019)

Crake, Angus; Christoforidis, Konstantinos C.; Gregg, Aoife; Moss, Benjamin; Kafizas, Andreas; Petit, Camille

doi:10.1002/smll.201970060

Cited by 3 publications

(1 citation statement)

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“…[12,[35][36][37][38][39] Particularly, some MOF and MOF composites can be used as desired precursors or templates to fabricate various heterostructural transitional metal/ metal oxides via a facile hydrothermal-calcination strategy. [40][41][42][43][44][45][46] More importantly, these MOF derived heterostructures usually inherit the high porosity and tailorable morphologies of MOFs, making them very promising for catalytic applications. [36,[47][48][49] For example, Li et al used dual MOF MIL-68@ZIF as the precursor and prepared a sort of hollow-structured cubic-In 2 O 3 @ZnCo 2 O 4 heterojunction, which showed high activity for CO 2 photoreduction.…”

Section: Introductionmentioning

confidence: 99%

Hybrid MOF Template‐Directed Construction of Hollow‐Structured In₂O₃@ZrO₂ Heterostructure for Enhancing Hydrogenation of CO₂ to Methanol

Cui

Zhang

Zhou

et al. 2022

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of the 21st century. [2][3][4] Catalytic hydrogenation of CO 2 with renewable H 2 to value-added chemicals and clean fuels is considered to be one of the most promising ways to simultaneously relieve global warming and energy shortage. [5][6][7][8] In particular, CO 2 -to-methanol technology has been paid great attention because CH 3 OH not only is an alternative fuel but also can be used as a key intermediate for the production of other commodity chemicals, such as aromatics and olefins. [9][10][11] As a result, considering its practical application and economy efficiency, intense research efforts have been devoted to develop lowcost, efficient, and selective catalysts for CO 2 hydrogenation to methanol during the last few years. [12][13][14][15] The Cu-based catalysts, such as Cu/ ZrO 2 , Cu/CeO 2 /TiO x , and Cu/ZnO/Al 2 O 3 , have been extensively studied in methanol production, [16][17][18] but most of these catalysts still suffer from low selectivity and stability due to an intensive reverse watergas shift (RWGS) reaction and a waterinduced metal sintering. [15,19,20] In this regard, In 2 O 3 -based catalysts have emerged as promising candidates in methanol synthesis from the thermal hydrogenation of CO 2 . [21][22][23] Especially, when In 2 O 3 is supported on ZrO 2 , the methanol yield could further be dramatically increased because of the formation of oxygen vacancy or frustrated Lewis pairs at the In 2 O 3 /ZrO 2 interface. [22,[24][25][26][27][28] It is reported that ZrO 2 support can interact with In 2 O 3 and affect the adsorption and dissociation of CO 2 and H 2 , resulting in the change of the reaction pathways for the methanol formation. [21][22][23]26,29,30] For example, Javier et al. confirmed that the In 2 O 3 supported on monoclinic ZrO 2 (m-ZrO 2 ) can better activate CO 2 molecules because of its superior character of oxygen vacancies on In 2 O 3 in comparison with those on alumina and ceria. [27] Gong et al. also found that m-ZrO 2 can improve the electron density of In 2 O 3 , and the resulting electron-rich In 2 O 3 can promote H 2 dissociation and the conversion of formate (HCOO*) to methoxy (CH 3 O*). [29] Therefore, rational modulation of the electronic interactions, type, dimension, and nature of indium-zirconia interfaces is a very important strategy to improve their catalytic performance. [21,23,31]

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Section: Introductionmentioning

confidence: 99%

Hybrid MOF Template‐Directed Construction of Hollow‐Structured In₂O₃@ZrO₂ Heterostructure for Enhancing Hydrogenation of CO₂ to Methanol

Cui

Zhang

Zhou

et al. 2022

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Tuning the Optoelectronic Properties of Hybrid Functionalized MIL-125-NH₂ for Photocatalytic Hydrogen Evolution

Mohammadnezhad

Kampouri

Wolff

et al. 2021

ACS Appl. Mater. Interfaces

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Metal–organic frameworks (MOFs) constructed with mixed ligands have shown great promise in the generation of materials with improved sorption, optical, and electronic properties. With an experimental, spectroscopic, and computational approach, herein, we investigated how the incorporation of different functionalized ligands within the structure of MIL-125-NH2 affects its performance in photocatalytic water reduction. We found that multiligand incorporation within the MOF structure has an impact on the light absorption spectrum and the electronic structure. These combined modifications improve the photocatalytic performance of MIL-125-NH2, thereby increasing the rate of hydrogen evolution reaction. Of the four nanoparticle/MOF photocatalytic systems tested, we showed that the Pt/MIL-125-NH2/(OH)2 system (Pt nanoparticle plus MIL-125-NH2 with amino and dihydroxyl functionalized ligands) outperforms its counterpart Pt/MIL-125-NH2 system, attributed to the enhanced p−π conjugation between the lone pairs of O atoms and their aromatic ligands resulting in a red-shifted absorption spectrum and greater spatial distribution of electron density.

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Enhanced Visible-Light-Driven Hydrogen Production through MOF/MOF Heterojunctions

Kampouri

Ebrahim

Fumanal

et al. 2021

ACS Appl. Mater. Interfaces

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A strategy for enhancing the photocatalytic performance of MOF-based systems (MOF: metal−organic framework) is developed through the construction of MOF/ MOF heterojunctions. The combination of MIL-167 with MIL-125-NH 2 leads to the formation of MIL-167/MIL-125-NH 2 heterojunctions with improved optoelectronic properties and efficient charge separation. MIL-167/MIL-125-NH 2 outperforms its single components MIL-167 and MIL-125-NH 2 , in terms of photocatalytic H 2 production (455 versus 0.8 and 51.2 μmol h −1 g −1 , respectively), under visible-light irradiation, without the use of any cocatalysts. This is attributed to the appropriate band alignment of these MOFs, the enhanced visible-light absorption, and long charge separation within MIL-167/MIL-125-NH 2 . Our findings contribute to the discovery of novel MOF-based photocatalytic systems that can harvest solar energy and exhibit high catalytic activities in the absence of cocatalysts.

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MOF‐Based Heterojunctions: The Effect of Materials Architecture in TiO₂/MOF Composites on CO₂ Photoreduction and Charge Transfer (Small 11/2019)

Cited by 3 publications

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Hybrid MOF Template‐Directed Construction of Hollow‐Structured In₂O₃@ZrO₂ Heterostructure for Enhancing Hydrogenation of CO₂ to Methanol

Hybrid MOF Template‐Directed Construction of Hollow‐Structured In₂O₃@ZrO₂ Heterostructure for Enhancing Hydrogenation of CO₂ to Methanol

Tuning the Optoelectronic Properties of Hybrid Functionalized MIL-125-NH₂ for Photocatalytic Hydrogen Evolution

Enhanced Visible-Light-Driven Hydrogen Production through MOF/MOF Heterojunctions

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MOF‐Based Heterojunctions: The Effect of Materials Architecture in TiO2/MOF Composites on CO2 Photoreduction and Charge Transfer (Small 11/2019)

Cited by 3 publications

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Hybrid MOF Template‐Directed Construction of Hollow‐Structured In2O3@ZrO2 Heterostructure for Enhancing Hydrogenation of CO2 to Methanol

Hybrid MOF Template‐Directed Construction of Hollow‐Structured In2O3@ZrO2 Heterostructure for Enhancing Hydrogenation of CO2 to Methanol

Tuning the Optoelectronic Properties of Hybrid Functionalized MIL-125-NH2 for Photocatalytic Hydrogen Evolution

Enhanced Visible-Light-Driven Hydrogen Production through MOF/MOF Heterojunctions

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MOF‐Based Heterojunctions: The Effect of Materials Architecture in TiO₂/MOF Composites on CO₂ Photoreduction and Charge Transfer (Small 11/2019)

Hybrid MOF Template‐Directed Construction of Hollow‐Structured In₂O₃@ZrO₂ Heterostructure for Enhancing Hydrogenation of CO₂ to Methanol

Hybrid MOF Template‐Directed Construction of Hollow‐Structured In₂O₃@ZrO₂ Heterostructure for Enhancing Hydrogenation of CO₂ to Methanol

Tuning the Optoelectronic Properties of Hybrid Functionalized MIL-125-NH₂ for Photocatalytic Hydrogen Evolution