| NSF Org: |
DMR Division Of Materials Research |
| Recipient: |
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| Initial Amendment Date: | August 10, 2012 |
| Latest Amendment Date: | August 10, 2012 |
| Award Number: | 1231586 |
| Award Instrument: | Standard Grant |
| Program Manager: |
John Schlueter
jschluet@nsf.gov (703)292-7766 DMR Division Of Materials Research MPS Directorate for Mathematical and Physical Sciences |
| Start Date: | September 1, 2012 |
| End Date: | August 31, 2017 (Estimated) |
| Total Intended Award Amount: | $800,000.00 |
| Total Awarded Amount to Date: | $800,000.00 |
| Funds Obligated to Date: |
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| History of Investigator: |
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| Recipient Sponsored Research Office: |
W5510 FRANKS MELVILLE MEMORIAL LIBRARY STONY BROOK NY US 11794-0001 (631)632-9949 |
| Sponsor Congressional District: |
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| Primary Place of Performance: |
Stony Brook NY US 11794-2100 |
| Primary Place of
Performance Congressional District: |
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| Unique Entity Identifier (UEI): |
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| Parent UEI: |
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| NSF Program(s): |
DMR SHORT TERM SUPPORT, SOLID STATE & MATERIALS CHEMIS |
| Primary Program Source: |
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| Program Reference Code(s): |
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| Program Element Code(s): |
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| Award Agency Code: | 4900 |
| Fund Agency Code: | 4900 |
| Assistance Listing Number(s): | 47.049 |
ABSTRACT
TECHNICAL
High-pressure (HP) synthesis is considered specialized and labor-intensive with low throughput and success rates. By integrating the installed infrastructure for theory, HP synthesis, and property measurements at SBU with national synchrotron x-ray and neutron facilities, we aim to unlock the potential of HP as a routine tool for solid-state materials discovery and development. An ab initio evolutionary algorithm for crystal structure prediction provides structure-property relations that can be tested experimentally using in situ scattering techniques. In addition to the precise determination of electronic and catalytic properties, the experimental results provide a feedback loop that validates and improves the predictive capability of the computational search. This strategy is broadly applicable to HP exploratory synthesis, and particularly suitable in the search for oxynitride photocatalysts, since HP favors production of solids, rather than competing reactions that result in breakdown to gaseous products. Pressure also facilitates band gap engineering through careful control over the stoichiometry and the ordering of O/N in closed systems, something difficult to achieve with current ammonolysis routes used at ambient pressure. The development of active nano-gold co-catalysts allows us to rapidly test the activity of even small amounts of recovered material. The funding will train a new generation of young scientists; comfortable with a more integrated approach to materials development that utilizes computational and experimental high-pressure techniques as mainstream tools.
NON TECHNICAL
Although materials synthesis at high pressure has the potential to produce unprecedented and transformative materials, traditional approaches are specialized and labor-intensive, with comparatively low rates of throughput and discovery. By integrating theory, synthesis, and property measurements at Stony Brook with the nation's synchrotron X-ray and neutron facilities, we aim to unlock the potential of high pressure as a routine tool for solid-state materials discovery. Computational search will provide lists of target compositions along with their predicted properties. These targets can be synthesized using high throughput techniques prior to precise determinations of electronic and catalytic properties. These results constitute a feedback loop that provides insight into better predictive capability. This strategy is particularly suitable in the search for oxynitride photocatalysts for use in hydrogen production from sunlight and water. The application of pressure favors the formation of solids rather than competing reactions that result in breakdown to gaseous products, oxygen and nitrogen. The recent development of active nano-gold co-catalysts allows us to rapidly test the activity of even small amounts of recovered material. The funding will train a new generation of young scientists; comfortable with a more integrated approach to materials development that utilizes computational and experimental high-pressure techniques as mainstream tools.
PUBLICATIONS PRODUCED AS A RESULT OF THIS RESEARCH
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PROJECT OUTCOMES REPORT
Disclaimer
This Project Outcomes Report for the General Public is displayed verbatim as submitted by the Principal Investigator (PI) for this award. Any opinions, findings, and conclusions or recommendations expressed in this Report are those of the PI and do not necessarily reflect the views of the National Science Foundation; NSF has not approved or endorsed its content.
Intellectual merit
The achievements of the collaboration included close integration of theory for the targeting of compositions, atomic arrangements and electronic properties that are optimized for the overall splitting of water into hydrogen and oxygen by sunlight. Based on earlier promising work on oxynitride materials, there was particular emphasis on discovering compositions that cannot be made at ambient conditions but can be recovered from high pressure (HP). The HP apparatus also provides a closed environment that not only stabilizes materials not available from room pressure syntheses, but also allows the dialing in of oxygen/nitrogen ratios to fine tune electronic.
The materials, whose stability was predicted by theory, were then made in high pressure apparatus adapted to interface with very high energy, penetrating, x-ray beams so that theoretical predictions could be confirmed, providing an instant feedback loop to the theory group to further improve predictions.
Key components of this infrastructure developed include: 1) USPEX, a freely distributed universal structure prediction tool. 2) Installation of ab initio property prediction methods for catalytic water splitting, with special emphasis on incorporating the pressure variable. 3) Improved high-pressure experimental throughput by adopting novel multi-cell designs at synchrotron x-ray sources at US National Laboratories. 4) Development of reactive precursors to access materials synthesized at HP, which are shown to have high photocatalytic activity, at atmospheric pressure, thereby considerably lowering cost. 5) Improved ability to test small samples recovered from multi-sample experiments for band gap and photocatalytic properties, including the development of highly active co-catalysts based on nano-materials, and 6) Building in feedback with close integration of theory, and synthesis/structural characterization.
This theory-HP infrastructure facilitated the discovery of novel materials in the complete range of compositions between GaN-ZnO, which are capable of overall water splitting without the use of surface catalysts. Compound have been produced, only at HP and recovered for testing, In several oxide-nitride systems.
Broader outcomes
NSF supported PhD thesis research of Peichuan Shen (graduated F13), Shen Zhao (graduated F13), William Woerner (graduated F15) HA Naveen Dharmagunawardhane (graduated F16) Alwin James (expected graduation F2018) and Qiyuan Wu (graduated F16) and Mahdi Dharvi (graduated F2017). All students took classes in formal practical and theoretical crystallography course taught by the senior investigators, as well as USPEX structure prediction workshops. Joint weekly group meetings introduced students to diverse ideas and the integration of experimental and theoretical approaches to problem solving. Other than working intimately with the theory group, experimental students worked closely with high pressure groups at the Advanced Photon Source, IL, National Synchrotron Light Source in NY, and the Spallation Neutron Source, Oak Ridge, TN. Grad student Peichuan Shen built up the characterization tools that led to discovery of exceptionally active co-catalysts as part of this grant. The grant also provided 33% support for postdoc Xiangfeng Zhou who implemented changes in the USPEX code, based on feedback from the experimental program, and made this available to researchers free of charge.The grant also provided laboratory support for Stony Brook undergraduate students including Yan Zhu (2012-13; now in medical school, SBU), Tristan Catalano (2014-, SBU) and John (Kip) Daly (2015-). Kip attended a high pressure workshop for undergraduates and is applying for grad school for acceptance F2018.
All investigators incorporated results into courses, including “Impact of Materials on Environment” a new introductory undergraduate course, and “Introduction to Environmental Materials Engineering”. Local non-specialist audiences were introduced to this research through Stony Brook University’s Open Night Program at one of the monthly 7 PM Friday evening lectures, attended by 150-200 members of the public. Because of the broadly interdisciplinary nature of our research, the subject areas of theory, energy and the environment are popular topics. Many of the audience are Long Island high school teachers. The public presentations at SBU are particularly useful for engaging the community and bring research discoveries to a local level. After the open-night talks for example, members of research groups lead laboratory tours and field questions.
Last Modified: 11/30/2017
Modified by: John B Parise
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