Ultrafine IrNi Bimetals Encapsulated in Zeolitic Imidazolate Frameworks‐Derived Porous N‐Doped Carbon for Boosting Oxygen Evolution in Both Alkaline and Acidic Electrolytes

The zeolitic imidazolate frameworks ZIF-8 and ZIF-67 harbour a series of fascinating stimuli responsive properties. Looking at their responsitivity to hydrostatic pressure as stimulus, open questions exist regarding the isotropic compression with non-penetrating pressure transmitting media. By applying a state-of-the-art high-pressure powder X-ray diffraction setup, we revisit the high-pressure behaviour of ZIF-8 and ZIF-67 up to <i>p</i> = 0.4 GPa in small pressure increments. We observe a drastic, reversible change of high-pressure powder X-ray diffraction data at <i>p</i> = 0.3 GPa, discovering large volume structural flexibility in ZIF-8 and ZIF-67. Our results imply a shallow underlying energy landscape in ZIF-8 and ZIF-67, an observation that might point at rich polymorphism of ZIF-8 and ZIF-67, similar to ZIF-4(Zn).<br>

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Revisiting the High-Pressure Properties of the Metal-Organic Frameworks ZIF-8 and ZIF-67

10.26434/chemrxiv.13146278 ◽

2020 ◽

Author(s):

Pia Vervoorts ◽

Stefan Burger ◽

Karina Hemmer ◽

Gregor Kieslich

Keyword(s):

High Pressure ◽

State Of The Art ◽

Energy Landscape ◽

Structural Flexibility ◽

Zeolitic Imidazolate Frameworks ◽

Stimuli Responsive ◽

X Ray Diffraction ◽

X Ray ◽

Open Questions ◽

Metal Organic

The zeolitic imidazolate frameworks ZIF-8 and ZIF-67 harbour a series of fascinating stimuli responsive properties. Looking at their responsitivity to hydrostatic pressure as stimulus, open questions exist regarding the isotropic compression with non-penetrating pressure transmitting media. By applying a state-of-the-art high-pressure powder X-ray diffraction setup, we revisit the high-pressure behaviour of ZIF-8 and ZIF-67 up to <i>p</i> = 0.4 GPa in small pressure increments. We observe a drastic, reversible change of high-pressure powder X-ray diffraction data at <i>p</i> = 0.3 GPa, discovering large volume structural flexibility in ZIF-8 and ZIF-67. Our results imply a shallow underlying energy landscape in ZIF-8 and ZIF-67, an observation that might point at rich polymorphism of ZIF-8 and ZIF-67, similar to ZIF-4(Zn).<br>

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

10.26434/chemrxiv.7108706.v1 ◽

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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Towards a Design of Active Oxygen Evolution Catalysts: Insights from Automated Density Functional Theory Calculations and Machine Learning

10.26434/chemrxiv.7926869 ◽

2019 ◽

Author(s):

Seoin Back ◽

Kevin Tran ◽

Zachary Ulissi

Keyword(s):

Machine Learning ◽

Oxygen Evolution ◽

Active Sites ◽

Density Functional ◽

Chemical Space ◽

Density Functional Theory Calculations ◽

Catalyst Design ◽

Transition Metal Catalysts ◽

Oxide Materials ◽

Design Strategies

<div> <div> <div> <div><p>Developing active and stable oxygen evolution catalysts is a key to enabling various future energy technologies and the state-of-the-art catalyst is Ir-containing oxide materials. Understanding oxygen chemistry on oxide materials is significantly more complicated than studying transition metal catalysts for two reasons: the most stable surface coverage under reaction conditions is extremely important but difficult to understand without many detailed calculations, and there are many possible active sites and configurations on O* or OH* covered surfaces. We have developed an automated and high-throughput approach to solve this problem and predict OER overpotentials for arbitrary oxide surfaces. We demonstrate this for a number of previously-unstudied IrO2 and IrO3 polymorphs and their facets. We discovered that low index surfaces of IrO2 other than rutile (110) are more active than the most stable rutile (110), and we identified promising active sites of IrO2 and IrO3 that outperform rutile (110) by 0.2 V in theoretical overpotential. Based on findings from DFT calculations, we pro- vide catalyst design strategies to improve catalytic activity of Ir based catalysts and demonstrate a machine learning model capable of predicting surface coverages and site activity. This work highlights the importance of investigating unexplored chemical space to design promising catalysts.<br></p></div></div></div></div><div><div><div> </div> </div> </div>

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S Doping Optimized Intermediate Energetics of FeCoOOh for Enhanced Oxygen Evolution Catalytic Activity

SSRN Electronic Journal ◽

10.2139/ssrn.3736398 ◽

2020 ◽

Author(s):

Ding Yuan ◽

Yuhai Dou ◽

Chun-Ting He ◽

Linping Yu ◽

Li Xu ◽

...

Keyword(s):

Catalytic Activity ◽

Oxygen Evolution

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