|Photocatalysis||Electrocatalysis||Heterogeneous Catalysis||Laboratory Resources|
Our group has made significant contributions in the field of heterogeneous catalysis. We focus on understanding the underlying physical and chemical processes at work in heterogeneous catalytic systems and use this knowledge to guide us in the design of optimal catalysts.
Our computational work focuses on gaining a better understanding of chemical transformations and catalytic activity using ab initio methods and developing physically transparent models. Alloying allows tuning of the electronic and geometric structure of catalysts to enhance certain reactions or to inhibit side reactions. We have used density functional theory calculations to predict that nickel/tin alloys could limit carbon mobility on the surface thus improving coking tolerance in high-temperature fuel cells. We have also used density functional theory to show that Ag(100) surfaces are more selective toward the partial oxidation of ethylene compared to Ag(111), suggesting that nanostructures dominated by Ag(100) facets could improve selectivity. In both of these cases, we were able to successfully synthesize the appropriate catalytic structures and verify our model predictions.
Much of our experimental work is inspired by modeling which we use to identify the optimal active sites and optimal hybrid catalyst systems for chemical transformations. The next steps involve synthesis, characterization, and study of these catalysts in experimental reactor systems. Our material syntheses have involved perovskite oxides catalysts, ion-conducting solid oxide membranes, nickel-tin alloy nanoparticles, shape and size dependent silver nanoparticles, silver-platinum alloy nanoparticles, and many others. We characterize these materials with X-ray diffraction, Nitrogen physisorption, scanning/transmission electron microscopy, energy-dispersive X-ray spectroscopy, wavelength dispersive X-ray spectroscopy, UV-vis spectroscopy, IR spectroscopy, Raman spectroscopy, and others. We have studied many different heterogeneous reactions including oxidative methane conversion, hydrocarbon steam reforming, carbon monoxide oxidation, ethylene epoxidation, and water-gas shift reaction. Current members working in this area include Rawan Almallahi, James Wortman and Shawn Lu.
Uncovering electronic and geometric descriptors of chemical activity for metal alloys
and oxides using unsupervised machine learning.
J.A. Esterhuizen, B.R. Goldsmith, S. Linic, Chem Catalysis, 2021.
Stable and selective catalysts for propane dehydrogenation operating at thermodynamic limit.
A. H. Motagamwala, R. Almallahi, J. Wortman, V.O. Igenegbai, S. Linic, Science, 2021.
Theory-Guided Machine Learning Finds Geometric Structure-Property Relationships for
Chemisorption on Subsurface Alloys.
J. Esterhuizen, B. Goldsmith and S. Linic, Chem, 2020.
Oxidative coupling of methane over hybrid membrane/catalyst active centers:
chemical requirements for prolonged lifetime
V. Igenegbai, R. Almallahi, R. Meyer and S. Linic, ACS Energy Letters, 4, 1465-1470, 2019.
In search of membrane-catalyst materials for oxidative coupling of methane:
Performance and phase stability studies of gadolinium-doped barium cerate and the impact of Zr doping
V. Igenegbai, R. Meyer and S. Linic, Applied Catalysis B: Environmental, 230, 29–35, 2018.
Analyzing Relationships between Surface Perturbations and Local Reactivity
H. Xin, S. Linic, J. Chem. Phys., 144, 234704, 2016.
A Viewpoint on Direct Methane Conversion to Ethane and Ethylene Using Oxidative
Coupling on Solid Catalysts
B. Farrell, V. Igenegbai, and S. Linic, ACS Catalysis, 6, 4340, 2016.
Oxidative coupling of methane over mixed oxide catalysts designed for solid oxide membrane reactors
B. Farrell, S. Linic, Catalysis Science & Technology, 6, 4370, 2016.
Direct electrochemical oxidation of ethanol on SOFCs: improved carbon tolerance
of Ni anode by alloying
B. Farrell, S. Linic, Applied Catalysis B: Environmental, 183, 386, 2016.
Identifying optimal active sites for heterogeneous catalysis by metal alloys
based on molecular descriptors and electronic structure engineering.
A. Holewinski, H. Xin, E. Nikolla, S. Linic, Current Opinions in Chemical Engineering, 2, 312, 2013.
Electronic Structure Engineering in Heterogeneous Catalysis: Identifying Novel Alloy
Catalysts Based on Rapid Screening for Materials with Desired Electronic Properties
H. Xin, A. Holewinski, N. Schweitzer, E. Nikolla, S. Linic, Topics in Catalysis, 55, 376, 2012.
High Activity Carbide Supported Catalysts for Water Gas Shift
N. Schweitzer, J. Schaidle, E. Obiefune, X. Pan, S. Linic, L. Thompson, JACS, 133, 2378, 2011.
Overcoming limitation in the design of selective heterogeneous catalysts by
manipulating shape and size of catalytic particles: Epoxidation reactions on silver
S. Linic, P. Christopher, ChemCatChem, 2, 1061, 2010.
Exceptions to the d-band Model of Chemisorption on Metal Surfaces: The Dominant
Role of Repulsion between Adsorbate States and Metal d-states
H. Xin, S. Linic, J. Chem. Phys., 132, 221101, 2010.
Establishing relationships between the geometric structure and chemical reactivity
of alloy catalysts based on their measured electronic structure
N. Schweitzer, H. Xin, E. Nikolla, J. T. Miller, S. Linic, Top. Catal., 53, 348, 2010.
Developing Relationships between the Local Chemical Reactivity of Alloy Catalysts
and Physical Characteristics of Constituent Metal Elements
H. Xin, N. Schweitzer, E. Nikolla, S. Linic, J. Chem. Phys., 132, 111101, 2010.
Shape and size specific chemistry of Ag nanostructures in catalytic ethylene
P. Christopher, S. Linic, ChemCatChem, 2, 78, 2010.
Geometric and Electronic Characteristics of Active Sites on TiO2-supported Au
Nano-catalysts: Insights from First Principles
S. Laursen, S. Linic, PCCP, 11, 11006, 2009.
First-Principles Analysis of the Activity of Transition and Noble Metals in the
Direct Utilization of Hydrocarbon Fuels at SOFC Operating Conditions
D. B. Ingram, S. Linic, J. Electrochem. Soc., 156, B1457, 2009.
Two-Step Mechanism for Low-Temperature Oxidation of Vacancies in Graphene
J. M. Carlsson, F. Hanke, S. Linic, M. Scheffler, Phys. Rev. Lett., 102, 166104, 2009.
Comparative study of the kinetics of methane steam reforming on supported
Ni and Sn/Ni alloy catalysts: the impact of the formation of Ni alloy on chemistry
E. Nikolla, J. W. Schwank, S. Linic, J. Catal., 263, 220, 2009.
Strong chemical interactions between Au and off-stoichiometric defects on TiO2 as
a possible source of chemical activity of nano-sized Au supported on the oxide
S. Laursen, S. Linic, J. Phys. Chem. C, 113, 6689, 2009.
Measuring and Relating the Electronic Structures of Nonmodel Supported Catalytic
Materials to Their Performance
E. Nikolla, J. W. Schwank, S. Linic, JACS, 131, 2747, 2009.
Engineering Selectivity in Heterogeneous Catalysis: Ag Nanowires as Selective
Ethylene Epoxiation Catalysts
P. Christopher, S. Linic, JACS, 130, 11264, 2008.
Hydrocarbon steam reforming on Ni alloys at solid oxide fuel cell
E. Nikolla, J. W. Schwank, S. Linic, Catalysis Today, 136, 243, 2008.
Promotion of the long-term stability of reforming Ni catalysts by
E. Nikolla, J. W. Schwank, S. Linic, J. Catal., 250, 85, 2007.
Controlling carbon surface chemistry by alloying: Carbon tolerant reforming catalyst
E. Nikolla, A. Holewinski, J. Schwank, S. Linic, JACS, 128, 11354, 2006.
Oxidation catalysis by oxide-supported Au nanostructures: The role
of supports and the effect of external conditions
S. Laursen, S. Linic, Phys. Rev. Lett., 97, 026101, 2006.
Synthesis, structure, and reactions of stable oxametallacycles from styrene oxide
M. Enever, S. Linic, K. Uffalussy, J. M. Vohs, M. A. Barteau, J. Phys. Chem. B, 109, 2227, 2005.
Selectivity driven design of bimetallic ethylene epoxidation catalysts
from first principles
S. Linic, J. Jankowiak, M. A. Barteau, J. Catal., 224, 489, 2004.
Ethylene epoxidation on Ag: Identification of the crucial surface intermediate
by experimental and theoretical investigation of its electronic structure
S. Linic, H. Piao, K. Abid, M. A. Barteau, Angew. Chem. Int. Ed., 43, 2918, 2004.
On the mechanism of Cs-promotion in ethylene epoxidation on Ag
S. Linic, M. A. Barteau, JACS, 126, 8086, 2004.
Construction of a reaction coordinate and a microkinetic model for
ethylene epoxidation on silver from DFT calculations and surface science experiments
S. Linic, M. A. Barteau, J. Catal., 214, 200, 2003.
Control of ethylene epoxidation selectivity by surface oxametallacycle
S. Linic, M. A. Barteau, JACS, 125, 4034, 2003.
Synthesis of oxametallacycles from 2-iodoethanol on Ag(111) and the structure
dependence of their reactivity
S. Linic, M. A. Barteau, Langmuir, 18, 5197, 2002.
Formation of a Stable Surface Oxametallacycle that Produces Ethylene Oxide
S. Linic, M. A. Barteau, JACS, 124, 310, 2002.