Wayne State University



College of Liberal Arts & Sciences
Lumigen Instrument Center
L.I.C. - X-Ray Crystallography Laboratory
 

X-Ray Crystallography Laboratory

The newly renovated X-Ray Crystallography Core Facility is administered by Lumigen Instrument Center and is located in the basement of the A. Paul Schaap Chemistry Building. Dr. Cassie Ward is the core manager and is responsible for training, instrument service and maintenance, safety, fee-for-service analysis, and laboratory policy. Within this laboratory there are two X-ray powder diffractometers (Bruker D2 Phaser and Bruker D8 ADVANCE) used for powder and thin film material characterization and an X-ray single-crystal diffractometer (Bruker X8 APEX) used to determine small molecule structure.
 
 

The UV-vis and X-ray Photoelectron Spectroscopy Instrument

The UV-vis and X-ray photoelectron spectroscopy instrument (UPS/XPS) is an essential tool to quantify chemical elements and the bonding of atoms within the top 2-10 nm of the sample surface and to study the work function and valence band of new materials in the areas of electronics, sensors, nanomaterials, catalysis, and energy. The UPS/XPS is critical for current research at WSU for the development of next-generation electronics, biomedical applications (biosensing, harmonic sensing), and several energy applications (catalysis, fuel cells, lithium-ion batteries and energy sustainability). The Fisher Scientific Nexsa is located in the Lumigen Instrument Center (LIC) room 40 (NMR Laboratory). Researchers can submit samples for analysis or undergo training as part of the educational/training with major research instrumentation.

Time line of events:

9/12/2019: The UPS/XPS has arrived!!!

9/30/2019: Scheduled installation

12/1/2019: Started running samples for users

3/20/2020: Due to covid-19 LIC is closed

6/1/2020: XPS is back running samples for users

11/1/2020: The XPS is now open for training. Please contact the X-ray lab staff for training details
 

Publications:

  1. Rajendran, S.; Pilli, A.; Omolere, O.; Kelber, J.; Arava, L. M. R. "An All-Solid-State Battery with a Tailored Electrode-Electrolyte Interface using Surface Chemistry and Interlayer-Based Approaches" Chemistry of Material, 2021, Just Accepted (doi:10.1021/acs.chemmater.1c00747).

  2. Samira, S.; Camayang, J C. A.; Patel, K.; Gu, X. K.; Nikolla, E. "Modulating Catalytic Properties of Targeted Metal Cationic Centers in Nanstochiometric Mixed Metal Oxides for Electrochemical Oxygen Reduction" ACS Energy Letters, 2021, 6, 1065.

  3. Mutinda, S. I.; Batugedara, T. N.; Brown, B.; Adeniran, O.; Liu, Z.-F.; Brock, S. L., "Rh2P Activity at a Fraction of the Cost? Co2-xRhxP Nanoparticles as Electrocatalysts for the Hydrogen Evolution Reaction in Acidic Media". ACS Applied Energy Materials, 2021, 4, 946.

  4. Sanni, A. M.; Rury, A. S. "Kinetic Molecular Cationic Control of Defect-Induced Broadband Light Emission in 2D Hybrid Lead Iodide Perovskites". Journal of Physical Chemistry Letters, 2021, 12, 101.

  5. Hewa-Rahinduwage, C. C.; Geng, X.; Silva, K. L.; Niu, X.; Zhang, L.; Brock, S. L.; Luo, L. "Reversible Electrochemical Gelation of Metal Chalcogenide Quantum Dots". Journal of the American Chemical Society, 2020, 142, 12207.

  6. F. de L. e Freitas, L., Puértolas, B., Zhang, J., Wang, B., Hoffman, A. S., Bare, S. R., Pérez-Ramírez, J., Medlin, J. W., Nikolla, E. "Tunable Catalytic Performance of Palladium Nanoparticles for H2O2 Direct Synthesis via Surface-Bound Ligands". ACS Catalysis, 2020, 10, 5202.

  7. Dinesh K. Amarasinghe and Federico A. Rabuffetti "Bandshift Luminescence Thermometry Using Mn4+:Na4Mg(WO4)3 Phosphors". Chemistry of Materials. 2019, 31, 24, 10197.

User Groups:

Eranda Nikolla group - College of Engineering
Charles Winter group - Chemistry Department
Long Luo group - Chemistry Department
Aaron Rury group - Chemistry Department
Stephanie Brock group - Chemistry Department
Federico Rabuffetti group - Chemistry Department
Leela Arava group - College of Engineering
Guru Dinda group - College of Engineering
Applied Materials, Inc.

 

Acknowledgement Statement:

The Nexsa was procured with the National Science Foundation Major Research Instrumentation (NSF:MRI) grant. Please acknowledge this grant in publications, presentation, thesis, and dissertations. A suggested statement can read: "This work made use of the UPS/XPS that is partially funded by National Science Foundation #1849578."
 
 

Powder and Thin-Film X-Ray Diffraction Facility

The powder/thin-film X-ray diffractometer (PXRD) provides compositional analysis. Researchers in several areas, including organic and inorganic chemistry, materials chemistry, and biochemistry used PXRD to determine phase identification, crystallinity, lattice parameters, expansion tensors, phase transition, crystal structure refinement of materials, and thin-film thickness, density and roughness. The Lumigen Instrument Center (LIC) has two PXRDs; the D2 Phaser (Bruker) and the D8 Advance with a DAVINCI design (Bruker). The D2 Phaser is a simple bench top system with Cu source and Lynxeye detector. The D8 Advance has two radiation sources (Mo and Cu) to provide X-rays of different penetrating power, parallel beam mode option, high sensitivity with good energy resolution from a 2nd generation energy discriminating detector (Lynxeye XE-T), and five interchangeable stages. The various D8 Advance platforms includes air sensitive, temperature dependent (-193 and 900°C), and in situ electrode/battery X-ray diffraction and reflectivity experiments. First and higher orders material characterization of nanoparticles, thin films, structural materials, and next generation energy storage and batteries can be defined by PXDR and is critical in designing and developing new materials.


 
 
D2 Phaser
D8 Advance


 

Courses and Training

I. Required, non-credit. Training to competence on the X-ray diffraction instrument is the mandatory first step. The user is stepped through the standard operation procedure (SOP) developed by Dr. Ward. When competence has been demonstrated, the user is granted daytime use, with staff present. Twenty-four/seven status is granted to a user by Dr. Ward once he/she has demonstrated consistent and competent operation of the X-ray diffractometer. Six SOPs for the five stages and the D2 Phaser are available at the workstations and are accessible online, http://www.chem.wayne.edu/lumigen/x-ray-instruments.html

II. Optional, non-credit Workshops and Short Courses. X-ray diffraction workshops have been developed by Dr. Ward. Workshop topics include: X-ray diffraction basic concepts and thin-film and powder X-ray diffraction. How to use analysis programs (TOPAS, EVA, and GenX) will be covered in these workshops. Both lecture and lab components are included. The commercial programs (TOPAS and EVA) are provided to Wayne State researchers through licenses purchased by LIC. Attendance will include internal, industrial, and government users and clients, both current and prospective. Thus, these workshops expand beyond academic benefits to broader impacts and maximizing the use of the LIC.

TOPAS workshop offered in August 2018
Thin-film analysis offered in August 2018

Summer training workshops will be announced in February for summer 2020
 

Outreach and Collaboration

Monika Jansohn from Oakland University (a PUI), and Na4B, LLC, used the PXRD to characterize thin films that developed for her NSF Phase II SBIR Grant: Multi-Layer Ceramic Electrolyte Membrane (ML-CEM) for sodium batteries.

LIC staff provide personal and group tours to university, industry, and government researchers. The Archaeological Lab Analysis class (Fall 2017) toured the X-ray Crystallography Laboratory, and a collaboration with a student from Dr. Krysta Ryszewski's (Associate professor of Anthropology) research group was initiated. For the student's master's thesis, he worked along with Dr. Ward on samples collected at an old Detroit factory near the river, which resulted in a accepted publication. His experience included preparing the samples, measuring the powder diffraction using the D8 Advance, and using TOPAS and EVA for interpretation of the artifacts.

The Detroit Local Section of the American Chemical Society and Wayne State Chemistry hosted a 6th through 8th graders event from a local Detroit school, Neinas Dual Language Learning Academy, on March 15th, 2019. The day-long event included a career panel, chemistry demonstrations, and lab tours of the Lumigen Instrument Center provided by the LIC staff. We plan to again hold a similar event in March 2020.
 

Publications

  1. Amarasinghe, D. K., Perera, S. S., Rabuffetti, F. A. "Rotational Disorder in Scheelite-Type NaRE(MO4)2 (RE = Rare-Earth, Y; M= Mo, W)" Crystal Growth & Design, 2020, ASAP.

  2. Blakeney, K. J., Martin, P. D., Winter, C. H. "A Volatile Dialane Complex from Ring Expansion of an N-Heterocyclic Carbene and Its Use in the Thermal Atomic Layer Deposition of Aluminum Metal Films" Organometallics, 2020, ASAP.

  3. Davis, J. L., Silva, K. L., Brock, S. L. "Exploiting Kinetics for Assembly of Multicomponent Nanoparticle Networks with Programmable Control of Heterogeneity" Chemical Communications, 2020, 56, 458.

  4. Silva, K. L., Silmi, L., Brock, S. L. "Effect of Metal Ion Solubility on the Oxidative Assembly of Metal Sulfide Quantum Dots" The Journal of Chemical Physics, 2019, 151, 234715.

  5. Samira, S., Gu, X. K., Nikolla, E. "Design Strategies for Efficient Nonstoichiometric Mixed Metal Oxide Electrocatalysts: Correlating Measurable Oxide Properties to Electrocatalytic Properties" ACS Catalysis, 2019, 10, 516.

  6. Amarasinghe, D. K., Rabuffetti, F. A. "Bandshift Luminescence Thermometry Using Mn4+:Na4Mg(WO4)3 Phosphors" Chemistry of Materials, 2019, 31, 10197.

  7. Samira, S., Deshpande, S., Roberts, C. A., Nacy, A. M., Kubal, J., Matesic, K., Oesterling, O., Greeley, J. P., Nikolla, E. "Non-Precious Metal Catalysts for Tuning Discharge Product Distribution at Solid-Solid Interfaces of Aprotic Li-O2 Batteries" Chemistry of Materials, 2019, 31, 7300.

  8. Carneiro, J., Nikolla, E. "Nanoengineering of Solid Oxide Electrochemical Cell Technologies: An Outlook" Nano Research, 2019, 12, 2081.

  9. Dissanayake, K. T., Amarasinghe, D. K., Suescun, L., Rabuffetti, F. A. "Accessing Mixed-Halide Upconverters Using Heterohaloacetate Precursors" Chemistry of Materials, 2019, 31, 6262.

  10. Perera, S. S., Rabuffetti, F. A. "Dysprosium-Activated Scheelite-Type Oxides as Thermosensitive Phosphors" Journal of Materials Chemistry C, 2019, 7, 7601.

  11. Hettiarachchi, M. A., Abdelhamid, E., Nadgorny, B., Brock, S. L. "Anisotropic Manganese Antimonide Nanoparticle Formation by Solution-Solid-Solid Growth Mechanism: Consequence of Sodium Borohydride Addition Towards Reduced Surface Oxidation and Enhanced Magnetic Moment" Nanoscale, 2019, 11, 6886.

  12. Szlag, R. S., Suescun, L., Dhanapala, B. D., Rabuffetti, F. A. "Rubidium-Alkaline-Earth Trifluoroacetate Hybrids as Self-Fluorinating Single-Source Precursors to Mixed-Metal Fluorides" Inorganic Chemistry, 2019, 58, 3041.

  13. Wang, B., Zhang, J., Herrera, L. P., Medlin, J. W., Nikolla, E. "110th Anniversary: Fabrication of Inverted Pd@TiO2 Nanostructures for Selective Catalysis" Industrial & Engineering Chemistry Research, 2019, 58, 4032.

  14. Sanni, A. M., Lavan, S. N., Avramenko, A., Rabuffetti, F. A., Suescun, L., Rury, A. S. "Room-Temperature Broadband Light Emission from Hybrid Lead Iodide Perovskite-Like Quantum Wells: Terahertz Spectroscopic Investigation of Metastable Defects" Journal of Physical Chemistry Letters, 2019, 10, 1653.

  15. Sanni, A. M., Shuhag, S., Rury, A. S. "Probing Fabry-Perot Interference in Self-Assembled Excitonic Microcrystals with Subgap Light Emission" The Journal of Physical Chemistry C, 2019, 123, 23103.

  16. Samira, S., Camayang, J. C., Nacy, A. M., Diaz, M., Meira, S. M., Nikolla, E. "Electrochemical Oxygen Reduction on Layered Mixed Metal Oxides: Effect of B-Site Substitution" Journal of Electroanalytical Chemistry, 2019, 833, 480.

  17. Perera, S. S., Dissanayake, T., Rabuffetti, F. A. "Alkaline-Earth Fluorohalide Nanocrystals for Upconversion Thermometry" Journal of Luminescence, 2019, 207, 416.

  18. Mutinda, S., Li, D., Kay, J. Brock S. L. "Synthesis and Characterization of Co2–xRhxP Nanoparticles and Their Catalytic Activity Towards the Oxygen Evolution Reaction" Journal of Materials Chemistry A, 2018, 6, 12142.

  19. Dissanayake, K. T. and Rabuffetti, F. A. "Multicolor Emission in Chemically and Structurally Tunable Er:Yb:SrFX (X - Cl, Br) Upconverting Nanocrystals" Chemistry of Materials, 2018, 30, 2453.

  20. Blakeney, K. J., Winter, C. H. "Atomic Layer Deposition of Aluminum Metal Films Using a Thermally Stable Aluminum Hydride Reducing Agent" Chemistry of Materials, 2018, 30, 1844.

  21. Gu, X. K., Carneiro, J. S. A., Samira, S., Das, A., Ariyasingha, N. M., Nikolla, E. "Efficient Oxygen Electrocatalysis by Nanostructured Mixed-Metal Oxides", Journal of the American Chemical Society, 2018, 140, 8128.

  22. Kerrigan, M. M., Klesko, J. P., Blakeney, K. J., Winter, C. H. "Low Temperature, Selective Atomic Layer Deposition of Nickel Metal Films" ACS Applied Materials and Interfaces, 2018, 10, 14200.

  23. Blakeney, K. J., Martin, P. D., Winter, C. H. "Aluminum Dihydride Complexes and Their Unexpected Application in Atomic Layer Deposition of Titanium Carbonitride Films" Dalton Transactions, 2018, 48, 10897.

  24. Blakeney, K. J., Ward, C. L., Winter, C. H. "Atomic Layer Deposition of Tungsten-Rich Carbide Films Using WCl6 and AlH2 (tBuNCH2CH2NMe2)" ECS Transactions, 2018, 86, 41.

  25. Hewavitharana, I. K., Brock S. L. "Application of Aqueous-Based Covalent Crosslinking Strategies to the Formation of Metal Chalcogenide Gels and Aerogels" Zeitschrift für Physikalische Chemie, 2018, 232, 1691.

  26. Kerrigan, M. M., Klesko, J. P., Rupich, S. M., Dezelah, C. L., Kanjolia, R. K, Chabal, Y. J., Winter, C. H. "Substrate Selectivity in the Low Temperature Atomic Layer Deposition of Cobalt Metal Films from Bis(1, 4-di-tert-butyl-1, 3-diazadienyl)cobalt and Formic Acid" The Journal of Chemical Physics, 2017, 146, 052813.

  27. Kerrigan, M. M., Klesko, J. P., Winter, C. H. "Low Temperature, Selective Atomic Layer Deposition of Cobalt Metal Films Using Bis(1,4-di-tert-butyl-1,3-diazadienyl)cobalt and Alkylamine Precursors", Chemistry of Materials, 2017, 29, 7458.

  28. Liyanage, D. R., Li, D., Cheek, Q. B., Baydoun, H., Brock, S. L. "Synthesis and Oxygen Evolution Reaction (OER) Catalytic Performance of Ni2–xRuxP Nanocrystals: Enhancing Activity by Dilution of the Noble Metal" Journal of Materials Chemistry A, 2017, 5, 17609.

  29. Hewavitharana, I. K., Brock, S. L. "When Ligand Exchange Leads to Ion Exchange: Nanocrystal Facets Dictate the Outcome" ACS Nano, 2017, 11, 11217.

  30. Blakeney, K. J., Winter, C. H. "Thermal Atomic Layer Deposition of Tungsten Carbide Films from WCl6 and AlMe3" Journal of Vacuum Science and Technology A, 2017, 35, 01A104.

  31. Li, D., Baydoun, H., Kulikowski, B., Brock, S. L. "Boosting the Catalytic Performance of Iron Phosphide Nanorods for the Oxygen Evolution Reaction by Incorporation of Manganese" Chemistry of Materials, 2017, 29, 3048.

  32. Pimmachcharige, R., Zhang, Y., Regmi, R., Lawes, G., Brock, S. L. "Solution-Phase Growth Mechanism of Phosphorus-Doped Control on the Nanoscale" Journal of Materials Chemistry C, 2017, 5, 3352.

  33. Perera, S. S.*, Amarasinghe, D. K.*, Dissanayake, K. T., and Rabuffetti, F.A. (*equal contribution) "Average and Local Crystal Structure of β-Er:Yb:NaYF4 Upconverting Nanocrystals Probed by X-ray Total Scattering" Chemistry of Materials, 2017, 29, 6287.

  34. Dhanapala, D. B., Mannino, N. A., Mendoza, L. M., Dissanayke, K. T., Martin, P. D., Seuscun, L., Rabuffetti, F. A. "Synthesis of Bimetallic Trifluoroacetates Through A Crystallochemical Investigation of Their Monometallic Counterparts: The Case of (A, A')(CF3COO)2 • nH2O (A, A' = Mg, Ca, Sr, Ba, Mn)" Dalton Transactions, 2017, 46, 1420.

  35. Davis, J. L., Chalifoux, A. M., Brock, S. L. "Role of Crystal Structure and Chalcogenide Redox Properties on the Oxidative Assembly of Cadmium Chalcogenide Nanocrystals" Langmuir, 2017, 33, 9434.

  36. Dhanapala, D., Munasinghe, H. N., Suescun, L., Rabuffetti, F. A. "Bimetallic Trifluoroacetates as Single-Source Precursors for Alkali-Manganese Fluoroperovskites" Inorganic Chemistry, 2017, 56, 13311.

  37. Carneiro, J. S. A., Brocca, R. A., Lucena, M. L. R. S., Nikolla, E. "Optimizing Cathode Materials for Intermediate-Temperature Solid Oxide Fuel Cells (SOFCs): Oxygen Reduction on Nanostructured Lanthanum Nickelate Oxides" Applied Catalysis B: Environmental, 2017, 200, 106.

  38. Klesko, J. P., Kerrigan, M. M., Winter, C. H. "Low Temperature Thermal Atomic Layer Deposition of Cobalt Metal Films" Chemistry of Materials, 2016, 28, 700.

  39. Li, D., Baydoun, H., Verani, C. N., Brock, S. "Efficient Water Oxidation Using CoMnP Nanoparticles" Journal of the American Chemical Society, 2016, 138, 4006.

  40. Li, D., Arachchige, M. P., Kulikowski, B., Lawes, G., Seda, T., Brock, S. L. "Control of Composition and Size in Discrete CoxFe2–xP Nanoparticles: Consequences for Magnetic Properties" Chemistry of Materials, 2016, 28, 3920.

  41. Dissanayake, K. T., Rabuffetti, F. A. "Infrared-to-Visible Upconversion Luminescence in Er:Yb:SrFBr Nanocrystals" Journal of Materials Chemistry C, 2016, 4, 2447.

  42. Hettiarachchi, M. A., Abdelhamid, E., Nadgorny, B., Brock, S. L. "Synthesis of Colloidal MnSb Nanoparticles: Consequences of Size and Surface Characteristics on Magnetic Properties" Journal of Materials Chemistry C, 2016, 4, 6790.

  43. Dissanayake, K. T., Mendoza, L. M., Martin, P. D., Suescun, L., Rabuffetti, F. A. "Open-Framework Structures of Anhydrous Sr(CF3COO)2 and Ba(CF3COO)2" Inorganic Chemistry, 2016, 55, 170.

Acknowledgement Statement

The D8 Advance was procured with an National Science Foundation Major Research Instrumentation (NSF:MRI) grant. Please acknowledge this grant in publications, presentation, thesis, and dissertations. A suggested statement can read:
"This work made use of the PXDR facility that is partially funded by National Science Foundation #1427926."

Contact
Dr. Cassie Ward
X-ray Crystallography Lab Manager
Chemistry 61
(313) 577-2587

Dr. Sameera Perera
X-ray Lab Postdoc
Chemistry 135

Dr. Judy Westrick
Director of Lumigen Instrument Center
Chemistry 225
(313) 577-2579


 


  This website was last updated: May 11, 2021

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5101 Cass Ave, Detroit, MI 48202
313-577-7784

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