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Stafford, Christopher M.

Publications and source records attributed to Stafford, Christopher M..

Progress in development of characterization capabilities to evaluate candidate materials for direct air capture applications

As part of U.S. national efforts to combat the detrimental effect of global climate change, the National Institute of Standards and Technology (NIST) was recently tasked to support efforts in direct air capture (DAC) of carbon dioxide research and deployment. In order to develop test procedures, materials, and documentary standards, key characterization methods relevant to DAC materials have been investigated and used to identify desirable properties for a potential Standard Reference Material (SRM). Select amine-supported materials that previously showed potential for DAC applications have been characterized using commonly available laboratory methods. Further insights into the adsorption characteristics have been gained from developing and applying more specialized characterization tools ideal for probing low concentrations of carbon dioxide. A broad suite of capabilities that examine relevant properties under appropriate conditions gives the most profound insights into a material's specific performance. We advocate for even more specialized capabilities to be developed and standardized to quantitatively monitor the interactions of CO 2 with molecular species in complex and often disordered systems to advance DAC and support carbon dioxide reduction (CDR) in general.

carbon dioxide↗

Assessing Composite Structure in Metal–Organic Framework-Polymer Mixed-Matrix Membranes

Metal-organic frameworks (MOFs) are renowned for their tunable structure, porosity, and internal chemistry, with demonstrated applications in molecular separations, storage, and conversion. While they are widely usable, the powdery characteristics of MOF materials can be limiting for large-scale processing and implementation in devices. Incorporating MOF particles into polymer supports affords engineering solutions to overcome these issues, yet the nature of the resulting composites is difficult to assess. Here, in this work, we present spectroscopic and calorimetric methods that we believe help establish a holistic physicochemical picture of the composite structure using a series of Zr MOFs with different pore sizes as a testbed. Power law decays are observed in X-ray scattering profiles in low q-space ranging between 2.4 and 3.3, which we interpret as changes in scattering due to polymer infiltrating MOF particles. This interpretation is supported by solid-state nuclear magnetic resonance spectroscopy and differential scanning calorimetry measurements that identify populations of the MOF-associated polymer. Additionally, positron annihilation lifetime spectroscopy measurements collected on a series of composites with different MOF-polymer ratios show multiple decay constants, each correlated to a different free volume elements. In combination with the spectroscopic, calorimetric, and scattering results, we utilize the trends in decay constants as a function of polymer mass fraction to hypothesize a polymer infiltration mechanism whereby large pores are preferentially filled, followed by small pores and, later still, interstitial spaces between particles. Even with vigorous investigation of polymer, MOF, and interface characteristics, the complex and heterogeneous nature of the composites makes absolute structural assertions difficult. We envision that the approaches demonstrated here will be a useful foundation to assess and ultimately guide the design of future MOF-polymer composites.

36 MATERIALS SCIENCE↗