skip to main content
DOE PAGES title logo U.S. Department of Energy
Office of Scientific and Technical Information

Title: Perspective: Toward “synthesis by design”: Exploring atomic correlations during inorganic materials synthesis

Abstract

Synthesis of inorganic extended solids is a critical starting point from which real-world functional materials and their consequent technologies originate. However, unlike the rich mechanistic foundation of organic synthesis, with its underlying rules of assembly (e.g., functional groups and their reactivities), the synthesis of inorganic materials lacks an underpinning of such robust organizing principles. In the latter case, any such rules must account for the diversity of chemical species and bonding motifs inherent to inorganic materials and the potential impact of mass transport on kinetics, among other considerations. Without such assembly rules, there is less understanding, less predictive power, and ultimately less control of properties. Despite such hurdles, developing a mechanistic understanding for synthesis of inorganic extended solids would dramatically impact the range of new material discoveries and resulting new functionalities, warranting a broad call to explore what is possible. Here we discuss our recent approaches toward a mechanistic framework for the synthesis of bulk inorganic extended solids, in which either embryonic atomic correlations or fully developed phases in solutions or melts can be identified and tracked during product selection and crystallization. The approach hinges on the application of high-energy x-rays, with their penetrating power and large Q-range, to exploremore » reaction pathways in situ. We illustrate this process using two examples: directed assembly of Zr clusters in aqueous solution and total phase awareness during crystallization from K–Cu–S melts. These examples provide a glimpse of what we see as a larger vision, in which large scale simulations, data-driven science, and in situ studies of atomic correlations combine to accelerate materials discovery and synthesis, based on the assembly of well-defined, prenucleated atomic correlations.« less

Authors:
ORCiD logo [1]; ORCiD logo [2]
  1. Argonne National Lab. (ANL), Argonne, IL (United States). Chemical Sciences and Engineering Division
  2. Argonne National Lab. (ANL), Argonne, IL (United States). Materials Sciences Division
Publication Date:
Research Org.:
Argonne National Lab. (ANL), Argonne, IL (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
OSTI Identifier:
1352678
Grant/Contract Number:  
AC02-06CH11357
Resource Type:
Accepted Manuscript
Journal Name:
APL Materials
Additional Journal Information:
Journal Volume: 4; Journal Issue: 5; Journal ID: ISSN 2166-532X
Publisher:
American Institute of Physics (AIP)
Country of Publication:
United States
Language:
English
Subject:
36 MATERIALS SCIENCE; Materials synthesis; Materials properties; Crystal structure; Solid solutions; X-ray diffraction

Citation Formats

Soderholm, L., and Mitchell, J. F. Perspective: Toward “synthesis by design”: Exploring atomic correlations during inorganic materials synthesis. United States: N. p., 2016. Web. doi:10.1063/1.4952712.
Soderholm, L., & Mitchell, J. F. Perspective: Toward “synthesis by design”: Exploring atomic correlations during inorganic materials synthesis. United States. doi:10.1063/1.4952712.
Soderholm, L., and Mitchell, J. F. Thu . "Perspective: Toward “synthesis by design”: Exploring atomic correlations during inorganic materials synthesis". United States. doi:10.1063/1.4952712. https://www.osti.gov/servlets/purl/1352678.
@article{osti_1352678,
title = {Perspective: Toward “synthesis by design”: Exploring atomic correlations during inorganic materials synthesis},
author = {Soderholm, L. and Mitchell, J. F.},
abstractNote = {Synthesis of inorganic extended solids is a critical starting point from which real-world functional materials and their consequent technologies originate. However, unlike the rich mechanistic foundation of organic synthesis, with its underlying rules of assembly (e.g., functional groups and their reactivities), the synthesis of inorganic materials lacks an underpinning of such robust organizing principles. In the latter case, any such rules must account for the diversity of chemical species and bonding motifs inherent to inorganic materials and the potential impact of mass transport on kinetics, among other considerations. Without such assembly rules, there is less understanding, less predictive power, and ultimately less control of properties. Despite such hurdles, developing a mechanistic understanding for synthesis of inorganic extended solids would dramatically impact the range of new material discoveries and resulting new functionalities, warranting a broad call to explore what is possible. Here we discuss our recent approaches toward a mechanistic framework for the synthesis of bulk inorganic extended solids, in which either embryonic atomic correlations or fully developed phases in solutions or melts can be identified and tracked during product selection and crystallization. The approach hinges on the application of high-energy x-rays, with their penetrating power and large Q-range, to explore reaction pathways in situ. We illustrate this process using two examples: directed assembly of Zr clusters in aqueous solution and total phase awareness during crystallization from K–Cu–S melts. These examples provide a glimpse of what we see as a larger vision, in which large scale simulations, data-driven science, and in situ studies of atomic correlations combine to accelerate materials discovery and synthesis, based on the assembly of well-defined, prenucleated atomic correlations.},
doi = {10.1063/1.4952712},
journal = {APL Materials},
number = 5,
volume = 4,
place = {United States},
year = {2016},
month = {5}
}

Journal Article:
Free Publicly Available Full Text
Publisher's Version of Record

Citation Metrics:
Cited by: 6 works
Citation information provided by
Web of Science

Save / Share:

Works referenced in this record:

Metal Oxides and Oxysalts as Anode Materials for Li Ion Batteries
journal, March 2013

  • Reddy, M. V.; Subba Rao, G. V.; Chowdari, B. V. R.
  • Chemical Reviews, Vol. 113, Issue 7
  • DOI: 10.1021/cr3001884

Shape-Control and Electrocatalytic Activity-Enhancement of Pt-Based Bimetallic Nanocrystals
journal, March 2013

  • Porter, Nathan S.; Wu, Hong; Quan, Zewei
  • Accounts of Chemical Research, Vol. 46, Issue 8
  • DOI: 10.1021/ar3002238

Semiconducting Tin and Lead Iodide Perovskites with Organic Cations: Phase Transitions, High Mobilities, and Near-Infrared Photoluminescent Properties
journal, July 2013

  • Stoumpos, Constantinos C.; Malliakas, Christos D.; Kanatzidis, Mercouri G.
  • Inorganic Chemistry, Vol. 52, Issue 15, p. 9019-9038
  • DOI: 10.1021/ic401215x

Size Control, Shape Evolution, and Silica Coating of Near-Infrared-Emitting PbSe Quantum Dots
journal, June 2007

  • Tan, Timothy T.; Selvan, S. Tamil; Zhao, Lan
  • Chemistry of Materials, Vol. 19, Issue 13
  • DOI: 10.1021/cm061974e

Emergent Properties Resulting from Type-II Band Alignment in Semiconductor Nanoheterostructures
journal, November 2010

  • Lo, Shun S.; Mirkovic, Tihana; Chuang, Chi-Hung
  • Advanced Materials, Vol. 23, Issue 2
  • DOI: 10.1002/adma.201002290

Imaging Catalysts at Work: A Hierarchical Approach from the Macro- to the Meso- and Nano-scale
journal, November 2012

  • Grunwaldt, Jan-Dierk; Wagner, Jakob B.; Dunin-Borkowski, Rafal E.
  • ChemCatChem, Vol. 5, Issue 1
  • DOI: 10.1002/cctc.201200356

Colloidal Assembly via Shape Complementarity
journal, July 2010

  • Macfarlane, Robert J.; Mirkin, Chad A.
  • ChemPhysChem, Vol. 11, Issue 15, p. 3215-3217
  • DOI: 10.1002/cphc.201000389

Selenium Nanomaterials: Applications in Electronics, Catalysis and Sensors
journal, February 2014

  • Chaudhary, Savita; Mehta, S. K.
  • Journal of Nanoscience and Nanotechnology, Vol. 14, Issue 2
  • DOI: 10.1166/jnn.2014.9128

Coexistence of Weak Ferromagnetism and Ferroelectricity in the High Pressure LiNbO 3 -Type Phase of FeTiO 3
journal, July 2009


From serendipity to design of polyoxometalates at the nanoscale, aesthetic beauty and applications
journal, January 2012

  • Cronin, Leroy; Müller, Achim
  • Chemical Society Reviews, Vol. 41, Issue 22
  • DOI: 10.1039/c2cs90087d

Oxide electrochromics: An introduction to devices and materials
journal, April 2012


From the computer to the laboratory: materials discovery and design using first-principles calculations
journal, May 2012

  • Hautier, Geoffroy; Jain, Anubhav; Ong, Shyue Ping
  • Journal of Materials Science, Vol. 47, Issue 21
  • DOI: 10.1007/s10853-012-6424-0

Theoretical Prediction and Experimental Realization of New Stable Inorganic Materials Using the Inverse Design Approach
journal, June 2013

  • Zakutayev, Andriy; Zhang, Xiuwen; Nagaraja, Arpun
  • Journal of the American Chemical Society, Vol. 135, Issue 27
  • DOI: 10.1021/ja311599g

Theoretical Prediction and Experimental Confirmation of Unusual Ternary Ordered Semiconductor Compounds in Sr–Pb–S System
journal, January 2014

  • Hao, Shiqiang; Zhao, Li-Dong; Chen, Chang-Qiang
  • Journal of the American Chemical Society, Vol. 136, Issue 4
  • DOI: 10.1021/ja411857y

Prediction and accelerated laboratory discovery of previously unknown 18-electron ABX compounds
journal, March 2015

  • Gautier, Romain; Zhang, Xiuwen; Hu, Linhua
  • Nature Chemistry, Vol. 7, Issue 4
  • DOI: 10.1038/nchem.2207

Magnetotransport of single crystalline YSb
journal, May 2016


Commentary: The Materials Project: A materials genome approach to accelerating materials innovation
journal, July 2013

  • Jain, Anubhav; Ong, Shyue Ping; Hautier, Geoffroy
  • APL Materials, Vol. 1, Issue 1
  • DOI: 10.1063/1.4812323

Python Materials Genomics (pymatgen): A robust, open-source python library for materials analysis
journal, February 2013


AFLOW: An automatic framework for high-throughput materials discovery
journal, June 2012


Looking for design in materials design
journal, October 2004

  • Eberhart, M. E.; Clougherty, D. P.
  • Nature Materials, Vol. 3, Issue 10
  • DOI: 10.1038/nmat1229

“Design” in Chemical Synthesis—An Illusion?
journal, May 2006

  • Jansen, Martin; Schön, J. Christian
  • Angewandte Chemie International Edition, Vol. 45, Issue 21
  • DOI: 10.1002/anie.200504510

Prenucleation clusters and non-classical nucleation
journal, December 2011


Pre-nucleation clusters as solute precursors in crystallisation
journal, January 2014

  • Gebauer, Denis; Kellermeier, Matthias; Gale, Julian D.
  • Chem. Soc. Rev., Vol. 43, Issue 7
  • DOI: 10.1039/c3cs60451a

The Problem with Determining Atomic Structure at the Nanoscale
journal, April 2007


Determination of actinide speciation in solution using high-energy X-ray scattering
journal, July 2005

  • Soderholm, L.; Skanthakumar, S.; Neuefeind, J.
  • Analytical and Bioanalytical Chemistry, Vol. 383, Issue 1
  • DOI: 10.1007/s00216-005-3322-1

Studying Actinide Correlations in Solution using High-Energy X-ray Scattering
journal, January 2005


The Structure of the Plutonium Oxide Nanocluster [Pu38O56Cl54(H2O)8]14−
journal, January 2008

  • Soderholm, L.; Almond, Philip M.; Skanthakumar, S.
  • Angewandte Chemie International Edition, Vol. 47, Issue 2
  • DOI: 10.1002/anie.200704420

The mechanism of hydrolytic polymerization of zirconyl solutions
journal, January 1990


The crystal structure of zirconyl chloride octahydrate and zirconyl bromide octahydrate
journal, July 1956


Understanding the Role of Aqueous Solution Speciation and Its Application to the Directed Syntheses of Complex Oxidic Zr Chlorides and Sulfates
journal, September 2013

  • Hu, Yung-Jin; Knope, Karah E.; Skanthakumar, S.
  • Journal of the American Chemical Society, Vol. 135, Issue 38
  • DOI: 10.1021/ja405555h

A Comparison of Neptunyl(V) and Neptunyl(VI) Solution Coordination: The Stability of Cation−Cation Interactions
journal, June 2008

  • Skanthakumar, S.; Antonio, Mark R.; Soderholm, L.
  • Inorganic Chemistry, Vol. 47, Issue 11
  • DOI: 10.1021/ic702478w

Structures and Energetics of Erbium Chloride Complexes in Aqueous Solution
journal, June 2009

  • Soderholm, L.; Skanthakumar, S.; Wilson, Richard E.
  • The Journal of Physical Chemistry A, Vol. 113, Issue 22
  • DOI: 10.1021/jp9012366

Changing Hafnium Speciation in Aqueous Sulfate Solutions: A High-Energy X-ray Scattering Study
journal, May 2014

  • Kalaji, Ali; Skanthakumar, S.; Kanatzidis, Mercouri G.
  • Inorganic Chemistry, Vol. 53, Issue 12
  • DOI: 10.1021/ic500938k

A novel nonanuclear hafnium oxide–hydroxide–sulphate cluster crystallised from aqueous solution
journal, January 2014


Aqueous Hafnium Sulfate Chemistry: Structures of Crystalline Precipitates
journal, September 2014

  • Kalaji, Ali; Soderholm, L.
  • Inorganic Chemistry, Vol. 53, Issue 20
  • DOI: 10.1021/ic501841e

Growth of single crystals from metallic fluxes
journal, June 1992


The Metal Flux: A Preparative Tool for the Exploration of Intermetallic Compounds
journal, November 2005

  • Kanatzidis, Mercouri G.; Pöttgen, Rainer; Jeitschko, Wolfgang
  • Angewandte Chemie International Edition, Vol. 44, Issue 43
  • DOI: 10.1002/anie.200462170

In situ studies of a platform for metastable inorganic crystal growth and materials discovery
journal, July 2014

  • Shoemaker, D. P.; Hu, Y. -J.; Chung, D. Y.
  • Proceedings of the National Academy of Sciences, Vol. 111, Issue 30
  • DOI: 10.1073/pnas.1406211111

Understanding Fluxes as Media for Directed Synthesis: In Situ Local Structure of Molten Potassium Polysulfides
journal, May 2012

  • Shoemaker, Daniel P.; Chung, Duck Young; Mitchell, J. F.
  • Journal of the American Chemical Society, Vol. 134, Issue 22
  • DOI: 10.1021/ja303047e

Stable Prenucleation Calcium Carbonate Clusters
journal, December 2008


Nucleation and growth of magnetite from solution
journal, February 2013

  • Baumgartner, Jens; Dey, Archan; Bomans, Paul H. H.
  • Nature Materials, Vol. 12, Issue 4
  • DOI: 10.1038/nmat3558

Characterizing Structure Through Shape Matching and Applications to Self-Assembly
journal, March 2011


Characterizing complex particle morphologies through shape matching: Descriptors, applications, and algorithms
journal, July 2011

  • Keys, Aaron S.; Iacovella, Christopher R.; Glotzer, Sharon C.
  • Journal of Computational Physics, Vol. 230, Issue 17
  • DOI: 10.1016/j.jcp.2011.04.017

    Works referencing / citing this record:

    A Hydride Route to Ternary Alkali Metal Borides: A Case Study of Lithium Nickel Borides
    journal, February 2019

    • Gvozdetskyi, Volodymyr; Hanrahan, Michael P.; Ribeiro, Raquel A.
    • Chemistry – A European Journal, Vol. 25, Issue 16
    • DOI: 10.1002/chem.201805398

    Formation Mechanism of Epitaxial Palladium–Platinum Core–Shell Nanocatalysts in a One‐Step Supercritical Synthesis
    journal, April 2019

    • Broge, Nils L. N.; Søndergaard‐Pedersen, Frederik; Sommer, Sanna
    • Advanced Functional Materials, Vol. 29, Issue 31
    • DOI: 10.1002/adfm.201902214

    Formation Mechanism of Epitaxial Palladium–Platinum Core–Shell Nanocatalysts in a One‐Step Supercritical Synthesis
    journal, April 2019

    • Broge, Nils L. N.; Søndergaard‐Pedersen, Frederik; Sommer, Sanna
    • Advanced Functional Materials, Vol. 29, Issue 31
    • DOI: 10.1002/adfm.201902214

    A Hydride Route to Ternary Alkali Metal Borides: A Case Study of Lithium Nickel Borides
    journal, February 2019

    • Gvozdetskyi, Volodymyr; Hanrahan, Michael P.; Ribeiro, Raquel A.
    • Chemistry – A European Journal, Vol. 25, Issue 16
    • DOI: 10.1002/chem.201805398