Temperature modulation of defects in NH<sub>2</sub>-UiO-66(Zr) for photocatalytic CO<sub>2</sub> reduction

Fu, Yanghe; Wu, Jiahui; Du, Rongfei; Guo, Ke; Ma, Rui; Zhang, Fumin; Zhu, Weidong; Fan, Maohong

doi:10.1039/c9ra08097j

Cited by 66 publications

(27 citation statements)

References 41 publications

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“…The formation depends on the reaction conditions of specific procedures. High concentrations of defect structures can result in the formation of large-scale defects through cluster missing (Shearer et al, 2016;Fu et al, 2019). Such large-scale defects are usually of high dimensions, resulting in the generation of mesoporous structures.…”

Section: Classificationmentioning

confidence: 99%

Defect Engineering in Metal‒Organic Frameworks as Futuristic Options for Purification of Pollutants in an Aqueous Environment

Cao

et al. 2021

Front. Chem.

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Clean water scarcity is becoming an increasingly important worldwide issue. The water treatment industry is demanding the development of novel effective materials. Defect engineering in nanoparticles is among the most revolutionary of technologies. Because of their high surface area, structural diversity, and tailorable ability, Metal‒Organic Frameworks (MOFs) can be used for a variety of purposes including separation, storage, sensing, drug delivery, and many other issues. The application in wastewater treatment associated with water stable MOF‒based materials has been an emerging research topic in recent decades. Defect engineering is a sophisticated technique used to manufacture defects and to change the geometric framework of target compounds. Since MOFs have a series of designable structures and active sites, tailoring properties in MOFs by defect engineering is a novel concept. Defect engineering can excavate hidden active sites in MOFs, which can lead to better performance in many fields. Therefore, this technology will open new opportunities in water purification processes. However, there has been little effort to comprehensively discuss this topic. In this review, we provide an overview of the development of defect engineered MOFs for water purification processes. Furthermore, we discuss the potential applications of defect engineered materials.

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Section: Classificationmentioning

confidence: 99%

Defect Engineering in Metal‒Organic Frameworks as Futuristic Options for Purification of Pollutants in an Aqueous Environment

Cao

et al. 2021

Front. Chem.

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“…This drawback can be overcome using zirconium-MOFs as electrocatalytic materials, in which the strength of Zr–O provides highly stable coordination network capable of withstand demanding reaction conditions 11 . Nonetheless, when using Zr-based metal–organic materials the reaction progress is limited to the formation of less reduced products such as formic acid 12 , 13 .…”

Section: Introductionmentioning

confidence: 99%

Copper(II) invigorated EHU-30 for continuous electroreduction of CO2 into value-added chemicals

Landaluce

Perfecto-Irigaray

Albo

et al. 2022

Sci Rep

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The doping of zirconium based EHU-30 and EHU-30-NH2 metal–organic frameworks with copper(II) yielded a homogeneous distribution of the dopant with a copper/zirconium ratio of 0.04–0.05. The doping mechanism is analysed by chemical analysis, microstructural analysis and pair distribution function (PDF) analysis of synchrotron total scattering data in order to get deeper insight into the local structure. According to these data, the Cu(II) atoms are assembled within the secondary building unit by a transmetalation reaction, contrarily to UiO-66 series in which the post-synthetic metalation of the MOF takes place through chemical anchorage. The resulting materials doubled the overall performance of the parent compounds for the CO2 electroreduction, while retained stable the performance during continuous transformation reaction.

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“…Defective Zr-MOF UIO-66 (named as Zr H, H stands for treatment with hydrochloric acid) was synthesized on the basis of a recent report with slight modification. [32,35,36] Briefly, 1,4-phthalic acid (H 2 BDC, 1.276 g) and zirconium(IV) oxynitrate dihydrate (ZrO(NO 3 ) 2 ÁxH 2 O, 1.65 g) were dissolved into N,N-dimethyl formamide (DMF, 36 ml), and then concentrated hydrochloric acid (36 wt%, 10 ml) was added. The solution was poured into a sealed Pyrex round bottom flask (maximum volume 100 ml), and the flask was heated in a silicone oil bath at 100 C for 30 min (which was the shortest time required for Zr H crystallization).…”

Section: Synthesis Of Defective Zr-mof and Defect-free Uio-66(zr)mentioning

confidence: 99%

“…Further, Vermoortele et al used high temperature removal modulator (TFA) to obtain UiO‐66 with high concentration of defects [ 33 ] and produced unsaturated sites as highly reactive Lewis acid sites, which showed enhanced catalytic performance in the “ene”‐type cyclization of citronellal isopulegol. Correspondingly, Fu et al synthesized NH 2 ‐UIO‐66(Zr) with different degrees of defects by controlling the synthesis temperature with hydrochloric acid as the modifying agent, [ 35 ] and Chelsea et al prepared different degrees of defects by adjusting the concentration of hydrochloric acid (modulator). [ 36 ] These defective MOFs showed greatly enhanced photocatalytic activity for CO 2 reduction and superior performance in the adsorption of organic pollutants.…”

Section: Introductionmentioning

confidence: 99%

Synthesis of defected UIO‐66 with boosting the catalytic performance via rapid crystallization

Chu

Guo

Wang

et al. 2021

Applied Organom Chemis

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Due to environmental and health concerns, it is very important to develop high activity oxidative desulfurization (ODS) catalyst for petroleum purification. Recently, defect engineering of metal organic frameworks (MOFs) to generate a large number of unsaturated catalytic active sites is a very promising approach. Defective MOF has good research value as ODS catalyst. Here, UIO‐66 with lots of defects can be prepared by rapid crystallization using concentrated hydrochloric acid as a modulator. The prepared UIO‐66 material has good industrial applicability due to its low synthesis temperature (100°C), short synthesis time (20–30 min), large‐scale preparation, and excellent catalytic performance (dibenzothiophene can be entirely removed in 6 min under the optimal catalytic conditions [25‐mg catalyst, 60°C, O/S 7.5]). The obtained material exhibits not only extraordinary ODS activity of 37.6 mmol h−1 g−1 but also good cycle stability for the removal of DBT (in 7 cycles without significant loss of activity, greater than 90.2%). And for large space volume 4,6‐DMDBT, it also shows excellent catalytic performance. The ODS mechanism of defect UIO‐66 for DBT is explored, and it proves that hydroxyl radicals and superoxide radicals are generated and play a critical role in ODS reaction. The excellent catalytic performance of defect UIO‐66 gives mainly the credit to the abundant defect sites, large specific surface area, and pore volume.

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Temperature modulation of defects in NH₂-UiO-66(Zr) for photocatalytic CO₂ reduction

Abstract: NH2-UiO-66(Zr) materials with structural defects, prepared by simply controlling the synthesis temperature, exhibit significantly enhanced activities in photocatalytic CO2 reduction.

Cited by 66 publications

References 41 publications

Defect Engineering in Metal‒Organic Frameworks as Futuristic Options for Purification of Pollutants in an Aqueous Environment

Defect Engineering in Metal‒Organic Frameworks as Futuristic Options for Purification of Pollutants in an Aqueous Environment

Copper(II) invigorated EHU-30 for continuous electroreduction of CO2 into value-added chemicals

Synthesis of defected UIO‐66 with boosting the catalytic performance via rapid crystallization

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Temperature modulation of defects in NH2-UiO-66(Zr) for photocatalytic CO2 reduction

Abstract: NH2-UiO-66(Zr) materials with structural defects, prepared by simply controlling the synthesis temperature, exhibit significantly enhanced activities in photocatalytic CO2 reduction.

Cited by 66 publications

References 41 publications

Defect Engineering in Metal‒Organic Frameworks as Futuristic Options for Purification of Pollutants in an Aqueous Environment

Defect Engineering in Metal‒Organic Frameworks as Futuristic Options for Purification of Pollutants in an Aqueous Environment

Copper(II) invigorated EHU-30 for continuous electroreduction of CO2 into value-added chemicals

Synthesis of defected UIO‐66 with boosting the catalytic performance via rapid crystallization

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Temperature modulation of defects in NH₂-UiO-66(Zr) for photocatalytic CO₂ reduction