Significant Gas Adsorption and Catalytic Performance by a Robust CuII-MOF Derived through Single-Crystal to Single-Crystal Transmetalation of a Thermally Less-Stable ZnII-MOF

2015 ◽  
Vol 21 (52) ◽  
pp. 19064-19070 ◽  
Author(s):  
Tapan K. Pal ◽  
Dinesh De ◽  
Subhadip Neogi ◽  
Pradip Pachfule ◽  
S. Senthilkumar ◽  
...  
Keyword(s):  
Single Crystal ◽  
Gas Adsorption ◽  
Catalytic Performance

Influence of Metal Substitution on the Pressure-Induced Phase Change in Flexible Zeolitic Imidazolate Frameworks

2018 ◽  
Author(s):  
C. Michael McGuirk ◽  
Tomče Runčevski ◽  
Julia Oktawiec ◽  
Ari Turkiewicz ◽  
mercedes K. taylor ◽  
...  
Keyword(s):  
Phase Change ◽  
Single Crystal ◽  
Gas Adsorption ◽  
High Capacity ◽  
Phase Changes ◽  
Zeolitic Imidazolate Frameworks ◽  
Metal Substitution ◽  
Heat Management ◽  
Metal Organic ◽  
First Time

<p>Metal–organic frameworks that display step-shaped adsorption profiles arising from discrete pressure-induced phase changes are promising materials for applications in both high-capacity gas storage and energy-efficient gas separations. The thorough investigation of such materials through chemical diversification, gas adsorption measurements, and <i>in situ </i>structural characterization is therefore crucial for broadening their utility. We examine a series of isoreticular, flexible zeolitic imidazolate frameworks (ZIFs) of the type M(bim)<sub>2</sub> (SOD; M = Zn<sup> </sup>(ZIF-7), Co (ZIF-9), Cd (CdIF-13); bim<sup>–</sup> = benzimidazolate), and elucidate the effects of metal substitution on the pressure-responsive phase changes and the resulting CO<sub>2</sub> and CH<sub>4</sub> step positions, pre-step uptakes, and step capacities. Using ZIF-7 as a benchmark, we reexamine the poorly understood structural transition responsible for its adsorption steps and, through high-pressure adsorption measurements, verify that it displays a step in its CH<sub>4 </sub>adsorption isotherms. The ZIF-9 material is shown to undergo an analogous phase change, yielding adsorption steps for CO<sub>2</sub> and CH<sub>4</sub> with similar profiles and capacities to ZIF-7, but with shifted threshold pressures. Further, the Cd<sup>2+</sup> analogue CdIF-13 is reported here for the first time, and shown to display adsorption behavior distinct from both ZIF-7 and ZIF-9, with negligible pre-step adsorption, a ~50% increase in CO<sub>2</sub> and CH<sub>4</sub> capacity, and dramatically higher threshold adsorption pressures. Remarkably, a single-crystal-to-single-crystal phase change to a pore-gated phase is also achieved with CdIF-13, providing insight into the phase change that yields step-shaped adsorption in these flexible ZIFs. Finally, we show that the endothermic phase change of these frameworks provides intrinsic heat management during gas adsorption. </p>

scholarly journals Playing with covalent triazine framework tiles for improved CO2 adsorption properties and catalytic performance

2019 ◽  
Vol 10 ◽  
pp. 1217-1227 ◽  
Author(s):  
Giulia Tuci ◽  
Andree Iemhoff ◽  
Housseinou Ba ◽  
Lapo Luconi ◽  
Andrea Rossin ◽  
...  
Keyword(s):  
Carbon Capture ◽  
Rational Design ◽  
Gas Adsorption ◽  
Ambient Pressure ◽  
Complex Structure ◽  
Building Blocks ◽  
Catalytic Performance ◽  
High Specific Surface Area ◽  
Morphological Properties ◽  
Design And Synthesis

The rational design and synthesis of covalent triazine frameworks (CTFs) from defined dicyano-aryl building blocks or their binary mixtures is of fundamental importance for a judicious tuning of the chemico-physical and morphological properties of this class of porous organic polymers. In fact, their gas adsorption capacity and their performance in a variety of catalytic transformations can be modulated through an appropriate selection of the building blocks. In this contribution, a set of five CTFs (CTF1–5) have been prepared under classical ionothermal conditions from single dicyano-aryl or heteroaryl systems. The as-prepared samples are highly micro-mesoporous and thermally stable materials featuring high specific surface area (up to 1860 m2·g−1) and N content (up to 29.1 wt %). All these features make them highly attractive samples for carbon capture and sequestration (CCS) applications. Indeed, selected polymers from this series rank among the CTFs with the highest CO2 uptake at ambient pressure reported so far in the literature (up to 5.23 and 3.83 mmol·g−1 at 273 and 298 K, respectively). Moreover, following our recent achievements in the field of steam- and oxygen-free dehydrogenation catalysis using CTFs as metal-free catalysts, the new samples with highest N contents have been scrutinized in the process to provide additional insights to their complex structure–activity relationship.

Rapid synthesis and catalytic performance of α-Mn2O3 single-crystal nanowires

2011 ◽  
Vol 46 (12) ◽  
pp. 1296-1302 ◽  
Author(s):  
Xinsong Yuan ◽  
Baojun Yang ◽  
Jianwen Hao ◽  
Xingming Hu ◽  
Jinmiao Zhu ◽  
...  
Keyword(s):  
Single Crystal ◽  
Catalytic Performance ◽  
Rapid Synthesis

Influence of Metal Substitution on the Pressure-Induced Phase Change in Flexible Zeolitic Imidazolate Frameworks

2018 ◽  
Author(s):  
C. Michael McGuirk ◽  
Tomče Runčevski ◽  
Julia Oktawiec ◽  
Ari Turkiewicz ◽  
mercedes K. taylor ◽  
...  
Keyword(s):  
Phase Change ◽  
Single Crystal ◽  
Gas Adsorption ◽  
High Capacity ◽  
Phase Changes ◽  
Zeolitic Imidazolate Frameworks ◽  
Metal Substitution ◽  
Heat Management ◽  
Metal Organic ◽  
First Time

<p>Metal–organic frameworks that display step-shaped adsorption profiles arising from discrete pressure-induced phase changes are promising materials for applications in both high-capacity gas storage and energy-efficient gas separations. The thorough investigation of such materials through chemical diversification, gas adsorption measurements, and <i>in situ </i>structural characterization is therefore crucial for broadening their utility. We examine a series of isoreticular, flexible zeolitic imidazolate frameworks (ZIFs) of the type M(bim)<sub>2</sub> (SOD; M = Zn<sup> </sup>(ZIF-7), Co (ZIF-9), Cd (CdIF-13); bim<sup>–</sup> = benzimidazolate), and elucidate the effects of metal substitution on the pressure-responsive phase changes and the resulting CO<sub>2</sub> and CH<sub>4</sub> step positions, pre-step uptakes, and step capacities. Using ZIF-7 as a benchmark, we reexamine the poorly understood structural transition responsible for its adsorption steps and, through high-pressure adsorption measurements, verify that it displays a step in its CH<sub>4 </sub>adsorption isotherms. The ZIF-9 material is shown to undergo an analogous phase change, yielding adsorption steps for CO<sub>2</sub> and CH<sub>4</sub> with similar profiles and capacities to ZIF-7, but with shifted threshold pressures. Further, the Cd<sup>2+</sup> analogue CdIF-13 is reported here for the first time, and shown to display adsorption behavior distinct from both ZIF-7 and ZIF-9, with negligible pre-step adsorption, a ~50% increase in CO<sub>2</sub> and CH<sub>4</sub> capacity, and dramatically higher threshold adsorption pressures. Remarkably, a single-crystal-to-single-crystal phase change to a pore-gated phase is also achieved with CdIF-13, providing insight into the phase change that yields step-shaped adsorption in these flexible ZIFs. Finally, we show that the endothermic phase change of these frameworks provides intrinsic heat management during gas adsorption. </p>

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