Variable Temperature and Pressure Operando MAS NMR for Catalysis Science and Related Materials

doi:https://doi.org/10.1021/acs.accounts.9b00557

Title: Variable Temperature and Pressure Operando MAS NMR for Catalysis Science and Related Materials

Full Record
Other Related Research

Abstract

The characterization of catalytic materials under working conditions is of paramount importance for a realistic depiction and comprehensive understanding of the system. Under such relevant environments, catalysts often exhibit properties or reactivity not observed under standard spectroscopic conditions. Fulfilling such harsh environments as high temperature and pressure is a particular challenge for solid-state NMR where samples spin several thousand times a second within a strong magnetic field. To address concerns of the disparities between spectroscopic environments and operando conditions, novel MAS NMR technology has been developed that enables the probing of catalytic systems over a wide range of pressures, temperatures, and chemical environments. In this account, new efforts to overcome the technical challenges in the development of operando MAS NMR will be briefly outlined. Emphasis will be placed on exploring the unique chemical regimes that take advantage of the new developments. With the progress achieved, it is possible to collect information on various nuclear constituents ( ¹H, ¹³C, ²³Na, ²⁷Al, etc.) as well as assess time-resolved interactions and transformations. Operando and in situ NMR enables the direct observation of chemical components and their interactions with active sites (such as Brønsted acid sites on zeolites) to reveal the nature of themore »« less

Authors:

^[1];

^[2];

^[1];

^[2]

Pacific Northwest National Lab. (PNNL), Richland, WA (United States); Washington State Univ., Pullman, WA (United States)
Pacific Northwest National Lab. (PNNL), Richland, WA (United States)

Publication Date:: 2020-01-13

Research Org.:: Pacific Northwest National Lab. (PNNL), Richland, WA (United States)

Sponsoring Org.:: USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences & Biosciences Division; National Institutes of Health (NIH)

OSTI Identifier:: 1633403

Report Number(s):: PNNL-SA-148734
Journal ID: ISSN 0001-4842

Grant/Contract Number:: AC05-76RL01830; R21ES029778

Resource Type:: Journal Article: Accepted Manuscript

Journal Name:: Accounts of Chemical Research

Additional Journal Information:: Journal Volume: 53; Journal Issue: 3; Journal ID: ISSN 0001-4842

Publisher:: American Chemical Society

Country of Publication:: United States

Language:: English

Subject:: 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; Alcohols; Chemical reactions; Nuclear magnetic resonance spectroscopy; Materials; Post-translational modification

Citation Formats


                    Jaegers, Nicholas R., Mueller, Karl T., Wang, Yong, and Hu, Jian Zhi. Variable Temperature and Pressure Operando MAS NMR for Catalysis Science and Related Materials.  United States: N. p., 2020. 
        Web.  doi:10.1021/acs.accounts.9b00557.

Copy to clipboard


                    Jaegers, Nicholas R., Mueller, Karl T., Wang, Yong, & Hu, Jian Zhi. Variable Temperature and Pressure Operando MAS NMR for Catalysis Science and Related Materials.  United States.  https://doi.org/10.1021/acs.accounts.9b00557

Copy to clipboard


                    Jaegers, Nicholas R., Mueller, Karl T., Wang, Yong, and Hu, Jian Zhi. Mon .  
        "Variable Temperature and Pressure Operando MAS NMR for Catalysis Science and Related Materials".  United States.  https://doi.org/10.1021/acs.accounts.9b00557.  https://www.osti.gov/servlets/purl/1633403.

Copy to clipboard


                    
@article{osti_1633403,

  title        = {Variable Temperature and Pressure Operando MAS NMR for Catalysis Science and Related Materials},

  author       = {Jaegers, Nicholas R. and Mueller, Karl T. and Wang, Yong and Hu, Jian Zhi},

  abstractNote = {The characterization of catalytic materials under working conditions is of paramount importance for a realistic depiction and comprehensive understanding of the system. Under such relevant environments, catalysts often exhibit properties or reactivity not observed under standard spectroscopic conditions. Fulfilling such harsh environments as high temperature and pressure is a particular challenge for solid-state NMR where samples spin several thousand times a second within a strong magnetic field. To address concerns of the disparities between spectroscopic environments and operando conditions, novel MAS NMR technology has been developed that enables the probing of catalytic systems over a wide range of pressures, temperatures, and chemical environments. In this account, new efforts to overcome the technical challenges in the development of operando MAS NMR will be briefly outlined. Emphasis will be placed on exploring the unique chemical regimes that take advantage of the new developments. With the progress achieved, it is possible to collect information on various nuclear constituents (1H, 13C, 23Na, 27Al, etc.) as well as assess time-resolved interactions and transformations. Operando and in situ NMR enables the direct observation of chemical components and their interactions with active sites (such as Brønsted acid sites on zeolites) to reveal the nature of the active center under catalytic conditions. Further, mixtures of such constituents can also be assessed to reveal the transformation of the active site when side products, such as water, are generated. These interactions are observed across a range of temperatures (-10 to 230 °C) and pressures (vacuum to 100 bar) for both vapor and condensed phase analysis. When coupled with 2D NMR, computational modeling, or both, specific binding modes are identified where the adsorbed state provides distinct signatures. In addition to vapor phase chemical environments, gaseous environments can be introduced and controlled over a wide range of pressures to support catalytic studies that require H2, CO, CO2, etc. Mixtures of three phases may also be employed. Such reactions can be monitored in situ to reveal the transformation of the substrates, active sites, intermediates, and products over the course of the study. Further, coupling of operando NMR with isotopic labeling schemes reveals specific mechanistic insights otherwise unavailable. Examples of these strategies will be outlined to reveal important fundamental insights on working catalyst systems possible only under operando conditions. Finally, extension of operando MAS NMR to study the solid–electrolyte interface and solvation structures associated with energy storage systems and biomedical systems will also be presented to highlight the versatility of this powerful technique.},

  doi          = {10.1021/acs.accounts.9b00557},

  url          = {https://www.osti.gov/biblio/1633403},
  journal      = {Accounts of Chemical Research},

  issn         = {0001-4842},

  number       = 3,

  volume       = 53,

  place        = {United States},

  year         = {2020},

  month        = {1}

}

Copy to clipboard

Journal Article:

Free Publicly Available Full Text

Accepted Manuscript (DOE)

Publisher's Version of Record

https://doi.org/10.1021/acs.accounts.9b00557

Other availability

Search WorldCat to find libraries that may hold this journal

Citation Metrics:

Cited by: 1 work

Citation information provided by
Web of Science

Save / Share:

Export Metadata

Save to My Library

Similar records in OSTI.GOV collections:

Annual Report: Fuels (30 September 2012)

Technical Report Link, Dirk ; Morreale, Bryan

The thermochemical conversion of fossil fuels through gasification will likely be the cornerstone of future energy and chemical processes due to its flexibility to accommodate numerous feeds (coal, biomass, natural gas, municipal waste, etc.) and to produce a variety of products (heat, specialty chemicals, power, etc.), as well as the inherent nature of the process to facilitate near zero emissions. Currently, the National Energy Technology Laboratory (NETL) Fuels Program has two pathways for syngas utilization: The production of transportation fuels, chemicals, or chemical intermediates. The hydrogen production as an intermediate for power production via advanced combustion turbines or fuel cells.more »« less
https://doi.org/10.2172/1098238

Full Text Available
Thermal perturbation of NMR properties in small polar and non-polar molecules

Journal Article Jaegers, Nicholas R. ; Wang, Yong ; Hu, Jian Z. - Scientific Reports

Water is an important constituent in an abundant number of chemical systems; however, its presence complicates the analysis of in situ ¹H MAS NMR investigations due to water’s ease of solidification and vaporization, the large changes in mobility, affinity for hydrogen bonding interactions, etc., that are reflected by dramatic changes in temperature-dependent chemical shielding. To understand the signatures of water and other small molecules in complex environments, in particular how water interacts with the other molecules, in this work the thermally-perturbed NMR properties of water are investigated in detail by in situ MAS NMR. Our results substantially extend the previouslymore »« less
https://doi.org/10.1038/s41598-020-63174-6

Full Text Available
Operando MAS NMR Reaction Studies at High Temperatures and Pressures

Journal Article Walter, Eric D. ; Qi, Long ; Chamas, Ali ; ... - Journal of Physical Chemistry C

Operando MAS-NMR studies provide unique insights into the details of chemical reactions; comprehensive information about temperature- and time-dependent changes in chemical species is accompanied by similarly rich information about changes in phase and chemical environment. Here we describe a new MAS-NMR rotor (the WHiMS rotor) capable of achieving internal pressures up to 400 bar at 20 °C or 225 bar at 250 °C, a range which includes many reactions of interest. The MAS-NMR spectroscopy enabled by these rotors is ideal for studying the behavior of mixed-phase systems, such as reactions involving solid catalysts and volatile liquids, with the potential tomore »« less
https://doi.org/10.1021/acs.jpcc.7b11442
Operando MAS NMR Reaction Studies at High Temperatures and Pressures

Journal Article Walter, Eric D. ; Qi, Long ; Chamas, Ali ; ... - Journal of Physical Chemistry. C

Operando MAS-NMR studies provide unique insights into the details of chemical reactions; comprehensive information about temperature- and time-dependent changes in chemical species is accompanied by similarly rich information about changes in phase and chemical environment. Here we describe a new MAS-NMR rotor (the WHiMS rotor) capable of achieving internal pressures up to 400 bar at 20 °C or 225 bar at 250 °C, a range which includes many reactions of interest. The MAS-NMR spectroscopy enabled by these rotors is ideal for studying the behavior of mixed-phase systems, such as reactions involving solid catalysts and volatile liquids, with the potential tomore »« less
https://doi.org/10.1021/acs.jpcc.7b11442
Nanocatalysis: Size- and Shape-dependent Chemisorption and Catalytic Reactivity

Technical Report Roldan-Cuenya, Beatriz ; Mistry, H. ; Choi, Y.

This review article focuses on correlating the catalytic reactivity of NPs and their geometry. It illustrated that chemisorption and catalytic properties such as the onset reaction temperature, the activity, and selectivity of a nanocatalyst may be tuned through controlled synthesis of NPs with well-defined sizes and shapes. It has become clear that detailed information on the physical/chemical properties of supported NP systems must be available for the rational design of the next generation of nanosized catalysts. Such NP systems must be representative of active catalysts, and must be sufficiently well-defined ( e.g., with respect to size and shape) to servemore »« less
https://doi.org/10.2172/1485534

Full Text Available

Similar Records