Probing the Surface Structure of Semiconductor Nanoparticles by DNP SENS with Dielectric Support Materials

Hanrahan, Michael P.; Chen, Yunhua; Blome-Fernández, Rafael; Stein, Jennifer L.; Pach, Gregory F.; Adamson, Marquix A.  S.; Neale, Nathan R.; Cossairt, Brandi M.; Vela, Javier; Rossini, Aaron J.

doi:10.1021/jacs.9b05509

Title: Probing the Surface Structure of Semiconductor Nanoparticles by DNP SENS with Dielectric Support Materials

Full Record
Other Related Research

Abstract

Surface characterization is crucial for understanding how the atomic-level structure affects the chemical and photophysical properties of semiconducting nanoparticles (NPs). Solid-state nuclear magnetic resonance spectroscopy (NMR) is potentially a powerful technique for the characterization of the surface of NPs, but it is hindered by poor sensitivity. Dynamic nuclear polarization surface enhanced NMR spectroscopy (DNP SENS) has previously been demonstrated to enhance the sensitivity of surface-selective solid-state NMR experiments by one to two orders of magnitude. Established sample preparations for DNP SENS experiments on NPs require the dilution of the NPs on mesoporous silica. Using hexagonal boron nitride (h-BN) to disperse the NPs doubles DNP enhancements and absolute sensitivity as compared to standard protocols with mesoporous silica. Alternatively, precipitating the NPs as powders, mixing them with h-BN, then impregnating the powdered mixture with radical solution leads to further four-fold sensitivity enhancements by increasing the concentration of NPs in the final sample. This modified procedure provides a factor 9 improvement in NMR sensitivity as compared to previously established DNP SENS procedures, enabling challenging homonuclear and heteronuclear 2D NMR experiments on CdS, Si and Cd3P2 NPs. These experiments allow NMR signals from the surface, sub-surface and core sites to be observed and assigned.more »« less

Authors:

Hanrahan, Michael P. ^[1]; Chen, Yunhua ^[1]; Blome-Fernández, Rafael ^[2];

^[3];

^[4]; Adamson, Marquix A. S. ^[2];

^[4]; Cossairt, Brandi M. ^[3];

^[1];

^[1]

Ames Lab., and Iowa State Univ., Ames, IA (United States). Dept. of Chemistry
Iowa State Univ., Ames, IA (United States). Dept. of Chemistry
Univ. of Washington, Seattle, WA (United States). Dept. of Chemistry
National Renewable Energy Lab. (NREL), Golden, CO (United States). Chemistry and Nanoscience Center

Publication Date:: Wed Aug 28 00:00:00 EDT 2019

Research Org.:: Ames Lab., Ames, IA (United States); National Renewable Energy Lab. (NREL), Golden, CO (United States)

Sponsoring Org.:: USDOE Office of Science (SC), Basic Energy Sciences (BES)

OSTI Identifier:: 1569744

Alternate Identifier(s):: OSTI ID: 1603261

Report Number(s):: IS-J-10034; NREL/JA-5900-73949
Journal ID: ISSN 0002-7863; TRN: US2001352

Grant/Contract Number:: AC02-07CH11358; AC36-08GO28308

Resource Type:: Accepted Manuscript

Journal Name:: Journal of the American Chemical Society

Additional Journal Information:: Journal Volume: 141; Journal Issue: 39; Journal ID: ISSN 0002-7863

Publisher:: American Chemical Society (ACS)

Country of Publication:: United States

Language:: English

Subject:: 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; 36 MATERIALS SCIENCE; 77 NANOSCIENCE AND NANOTECHNOLOGY; surface characterization; quantum dots; solid-state NMR spectroscopy; nanoparticles

Citation Formats


                    Hanrahan, Michael P., Chen, Yunhua, Blome-Fernández, Rafael, Stein, Jennifer L., Pach, Gregory F., Adamson, Marquix A.  S., Neale, Nathan R., Cossairt, Brandi M., Vela, Javier, and Rossini, Aaron J. Probing the Surface Structure of Semiconductor Nanoparticles by DNP SENS with Dielectric Support Materials.  United States: N. p., 2019. 
Web.  doi:10.1021/jacs.9b05509.

Copy to clipboard


                    Hanrahan, Michael P., Chen, Yunhua, Blome-Fernández, Rafael, Stein, Jennifer L., Pach, Gregory F., Adamson, Marquix A.  S., Neale, Nathan R., Cossairt, Brandi M., Vela, Javier, & Rossini, Aaron J. Probing the Surface Structure of Semiconductor Nanoparticles by DNP SENS with Dielectric Support Materials.  United States.  https://doi.org/10.1021/jacs.9b05509

Copy to clipboard


                    Hanrahan, Michael P., Chen, Yunhua, Blome-Fernández, Rafael, Stein, Jennifer L., Pach, Gregory F., Adamson, Marquix A.  S., Neale, Nathan R., Cossairt, Brandi M., Vela, Javier, and Rossini, Aaron J. Wed .  
"Probing the Surface Structure of Semiconductor Nanoparticles by DNP SENS with Dielectric Support Materials".  United States.  https://doi.org/10.1021/jacs.9b05509.  https://www.osti.gov/servlets/purl/1569744.

Copy to clipboard


                    
@article{osti_1569744,

  title        = {Probing the Surface Structure of Semiconductor Nanoparticles by DNP SENS with Dielectric Support Materials},

  author       = {Hanrahan, Michael P. and Chen, Yunhua and Blome-Fernández, Rafael and Stein, Jennifer L. and Pach, Gregory F. and Adamson, Marquix A.  S. and Neale, Nathan R. and Cossairt, Brandi M. and Vela, Javier and Rossini, Aaron J.},

  abstractNote = {Surface characterization is crucial for understanding how the atomic-level structure affects the chemical and photophysical properties of semiconducting nanoparticles (NPs). Solid-state nuclear magnetic resonance spectroscopy (NMR) is potentially a powerful technique for the characterization of the surface of NPs, but it is hindered by poor sensitivity. Dynamic nuclear polarization surface enhanced NMR spectroscopy (DNP SENS) has previously been demonstrated to enhance the sensitivity of surface-selective solid-state NMR experiments by one to two orders of magnitude. Established sample preparations for DNP SENS experiments on NPs require the dilution of the NPs on mesoporous silica. Using hexagonal boron nitride (h-BN) to disperse the NPs doubles DNP enhancements and absolute sensitivity as compared to standard protocols with mesoporous silica. Alternatively, precipitating the NPs as powders, mixing them with h-BN, then impregnating the powdered mixture with radical solution leads to further four-fold sensitivity enhancements by increasing the concentration of NPs in the final sample. This modified procedure provides a factor 9 improvement in NMR sensitivity as compared to previously established DNP SENS procedures, enabling challenging homonuclear and heteronuclear 2D NMR experiments on CdS, Si and Cd3P2 NPs. These experiments allow NMR signals from the surface, sub-surface and core sites to be observed and assigned. For example, we demonstrate that the acquisition of DNP-enhanced 2D 113Cd113Cd correlation NMR experiments on CdS NPs and natural isotropic abundance 2D 13C29Si HETCOR of functionalized Si NPs. These experiments provide a critical understanding of NP surface structures.},

  doi          = {10.1021/jacs.9b05509},

  journal      = {Journal of the American Chemical Society},

  number       = 39,

  volume       = 141,

  place        = {United States},

  year         = {Wed Aug 28 00:00:00 EDT 2019},

  month        = {Wed Aug 28 00:00:00 EDT 2019}

}

Copy to clipboard

Journal Article:

Free Publicly Available Full Text

Accepted Manuscript (DOE)

Publisher's Version of Record

https://doi.org/10.1021/jacs.9b05509

Other availability

Search WorldCat to find libraries that may hold this journal

Citation Metrics:

Cited by: 26 works

Citation information provided by
Web of Science

Save / Share:

Export Metadata

Save to My Library

Similar Records in DOE PAGES and OSTI.GOV collections:

Atomic-Level Structure of Mesoporous Hexagonal Boron Nitride Determined by High-Resolution Solid-State Multinuclear Magnetic Resonance Spectroscopy and Density Functional Theory Calculations

Journal Article Dorn, Rick W. ; Heintz, Patrick M. ; Hung, Ivan ; ... - Chemistry of Materials

Mesoporous hexagonal boron nitride (p-BN) has received significant attention over the last decade as a promising candidate for water cleaning/pollutant removal and hydrogen storage applications. Here, high-resolution solid-state NMR spectroscopy and plane-wave density-functional theory (DFT) calculations are used to obtain an atomic-level description of p-BN. ¹H–¹⁵N or ¹H–¹⁴N heteronuclear (HETCOR) correlation experiments recorded with either conventional NMR at room temperature or dynamic nuclear polarization surface-enhanced spectroscopy (DNP-SENS) at ca. 100 K reveal NB₂H, NBH₂, NBH₃⁺ species residing on the edges of BN sheets. Ultra-high field 35.2 T ¹¹B NMR spectroscopy was used to resolve ¹¹B NMR signals from BN₃, BN₂O_x(OH)_1–xmore »« less
https://doi.org/10.1021/acs.chemmater.1c03791

Full Text Available
Indirectly Detected DNP-Enhanced ¹⁷O NMR Spectroscopy: Observation of Non-Protonated Near-Surface Oxygen at Naturally Abundant Silica and Silica-Alumina

Journal Article Kobayashi, Takeshi ; Pruski, Marek - ChemPhysChem

Abstract Recent studies have shown that dynamic nuclear polarization (DNP) can be used to detect ¹⁷ O solid‐state NMR spectra of naturally abundant samples within a reasonable experimental time. Observations using indirect DNP, which relies on ¹ H mediation in transferring electron hyperpolarization to ¹⁷ O, are currently limited mostly to hydroxyls. Direct DNP schemes can hyperpolarize non‐protonated oxygen near the radicals; however, they generally offer much lower signal enhancements. In this study, we demonstrate the detection of signals from non‐protonated ¹⁷ O in materials containing silicon. The sensitivity boost that made the experiment possible originates from three sources: indirectmore »« less
https://doi.org/10.1002/cphc.202100290

Full Text Available
Indirectly detected chemical shift correlation NMR spectroscopy in solids under fast magic angle spinning

Thesis/Dissertation Mao, Kanmi

The development of fast magic angle spinning (MAS) opened up an opportunity for the indirect detection of insensitive low-γ nuclei (e.g., ¹³C and ¹⁵N) via the sensitive high-{gamma} nuclei (e.g., ¹H and ¹⁹F) in solid-state NMR, with advanced sensitivity and resolution. In this thesis, new methodology utilizing fast MAS is presented, including through-bond indirectly detected heteronuclear correlation (HETCOR) spectroscopy, which is assisted by multiple RF pulse sequences for ¹H-¹H homonuclear decoupling. Also presented is a simple new strategy for optimization of ¹H-¹H homonuclear decoupling. As applications, various classes of materials, such as catalytic nanoscale materials, biomolecules, and organic complexes, are studied by combining indirect detection and other one-dimensional (1D) and two-dimensional (2D) NMR techniques. Indirectly detected through-bond HETCOR spectroscopy utilizing refocused INEPT (INEPTR) mixing was developed under fast MAS (Chapter 2). The time performance of this approach in ¹H detected 2D ¹H{l_brace}¹³C{r_brace} spectra was significantly improved, by a factor of almost 10, compared to the traditional ¹³C detected experiments, as demonstrated by measuring naturally abundant organic-inorganic mesoporous hybrid materials. The through-bond scheme was demonstrated as a new analytical tool, which provides complementary structural information in solid-state systems in addition to through-space correlation. To further benefit the sensitivity of the INEPT transfer in rigid solids, the combined rotation and multiple-pulse spectroscopy (CRAMPS) was implemented for homonuclear ¹H decoupling under fast MAS (Chapter 3). Several decoupling schemes (PMLG5_m^{more » $$\bar{x}$$}, PMLG5_mm^$$\bar{x}$$x and SAM3) were analyzed to maximize the performance of through-bond transfer based on decoupling efficiency as well as scaling factors. Indirect detection with assistance of PMLG_m^$$\bar{x}$$ during INEPTR transfer proved to offer the highest sensitivity gains of 3-10. In addition, the CRAMPS sequence was applied under fast MAS to increase the ¹H resolution during t₁ evolution in the traditional, ¹³C detected HETCOR scheme. Two naturally abundant solids, tripeptide N-formyl-L-methionyl-L-leucyl-L-phenylalanine (f-MLF-OH) and brown coal, with well ordered and highly disordered structures, respectively, are studied to confirm the capabilities of these techniques. Concomitantly, a simple optimization of ¹H homonuclear dipolar decoupling at MAS rates exceeding 10 kHz was developed (Chapter 4). The fine-tuned decoupling efficiency can be obtained by minimizing the signal loss due to transverse relaxation in a simple spin-echo experiment, using directly the sample of interest. The excellent agreement between observed decoupling pattern and earlier theoretical predictions confirmed the utility of this strategy. The properties of naturally abundant surface-bound fluorocarbon groups in mesoporous silica nanoparticles (MSNs) were investigated by the above-mentioned multidimensional solid-state NMR experiments and theoretical modeling (Chapter 5). Two conformations of (pentafluorophenyl)propyl groups (abbreviated as PFP) were determined as PFP-prone and PFP-upright, whose aromatic rings are located above the siloxane bridges and in roughly upright position, respectively. Several 1D and 2D NMR techniques were implemented in the characterizations, including indirectly detected ¹H{l_brace}¹³C{r_brace} and ¹⁹F{l_brace}¹³C{r_brace} 2D HETCOR, Carr-Purcell-Meiboom-Gill (CPMG) assisted ²⁹Si direct polarization and ²⁹Si¹⁹F 2D experiments, 2D double-quantum (DQ) ¹⁹F MAS NMR spectra and spin-echo measurements. Furthermore, conformational details of two types of PFP were confirmed by theoretical calculation, operated by Dr. Takeshi Kobayashi. Finally, the arrangement of two surfactants, cetyltrimetylammoium bromide (CTAB) and cetylpyridinium bromide (CPB), mixed inside the MSN pores, was studied by solid-state NMR (Chapter 6). By analyzing the ¹H-¹H DQMAS and NOESY correlation spectra, the CTAB and CPB molecules were shown to co-exist inside the pores without forming significant monocomponent domains. A 'folded-over' conformation of CPB headgroups was proposed according to the results from ¹H-²⁹Si 2D HETCOR.« less
https://doi.org/10.2172/1029608

Full Text Available
Combining fast magic angle spinning dynamic nuclear polarization with indirect detection to further enhance the sensitivity of solid-state NMR spectroscopy

Journal Article Wang, Zhuoran ; Hanrahan, Michael P. ; Kobayashi, Takeshi ; ... - Solid State Nuclear Magnetic Resonance

Dynamic nuclear polarization (DNP) and indirect detection are two commonly applied approaches for enhancing the sensitivity of solid-state NMR spectroscopy. However, their use in tandem has not yet been investigated. With the advent of low-temperature fast magic angle spinning (MAS) probes with 1.3-mm diameter rotors capable of MAS at 40 kHz it becomes feasible to combine these two techniques. In this study, we performed DNP-enhanced 2D indirectly detected heteronuclear correlation (idHETCOR) experiments on ¹³C, ¹⁵N, ¹¹³Cd and ⁸⁹Y nuclei in functionalized mesoporous silica, CdS nanoparticles, and Y₂O₃ nanoparticles. The sensitivity of the 2D idHETCOR experiments was compared with those ofmore »« less
https://doi.org/10.1016/j.ssnmr.2020.101685

Full Text Available
Optimal sample formulations for DNP SENS: The importance of radical-surface interactions

Journal Article Perras, Frederic A. ; Wang, Lin-Lin ; Manzano, J. Sebastian ; ... - Current Opinion in Colloid & Interface Science

The efficacy of dynamic nuclear polarization (DNP) surface-enhanced NMR spectroscopy (SENS) is reviewed for alumina, silica, and ordered mesoporous carbon (OMC) materials, with vastly different surface areas, as a function of the biradical concentration. Importantly, our studies show that the use of a “one-size-fits-all” biradical concentration should be avoided when performing DNP SENS experiments and instead an optimal concentration should be selected as appropriate for the type of material studied as well as its surface area. In general, materials with greater surface areas require higher radical concentrations for best possible DNP performance. This result is explained with the use ofmore »« less
Cited by 41
https://doi.org/10.1016/j.cocis.2017.11.002

Full Text Available

Similar Records