John Mark P. Martirez
Princeton University
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Publication
Featured researches published by John Mark P. Martirez.
Proceedings of the National Academy of Sciences of the United States of America | 2016
Dayne F. Swearer; Hangqi Zhao; Linan Zhou; Chao Zhang; Hossein Robatjazi; John Mark P. Martirez; Caroline M. Krauter; Sadegh Yazdi; Michael J. McClain; Emilie Ringe; Emily A. Carter; Peter Nordlander; Naomi J. Halas
Significance Plasmon-enhanced photocatalysis holds significant promise for controlling chemical reaction rates and outcomes. Unfortunately, traditional plasmonic metals have limited surface chemistry, while conventional catalysts are poor optical absorbers. By placing a catalytic reactor particle adjacent to a plasmonic antenna, the highly efficient and tunable light-harvesting capacities of plasmonic nanoparticles can be exploited to drastically increase absorption and hot-carrier generation in the reactor nanoparticles. We demonstrate this antenna−reactor concept by showing that plasmonic aluminum nanocrystal antennas decorated with small catalytic palladium reactor particles exhibit dramatically increased photocatalytic activity over their individual components. The modularity of this approach provides for independent control of chemical and light-harvesting properties and paves the way for the rational, predictive design of efficient plasmonic photocatalysts. Metallic nanoparticles with strong optically resonant properties behave as nanoscale optical antennas, and have recently shown extraordinary promise as light-driven catalysts. Traditionally, however, heterogeneous catalysis has relied upon weakly light-absorbing metals such as Pd, Pt, Ru, or Rh to lower the activation energy for chemical reactions. Here we show that coupling a plasmonic nanoantenna directly to catalytic nanoparticles enables the light-induced generation of hot carriers within the catalyst nanoparticles, transforming the entire complex into an efficient light-controlled reactive catalyst. In Pd-decorated Al nanocrystals, photocatalytic hydrogen desorption closely follows the antenna-induced local absorption cross-section of the Pd islands, and a supralinear power dependence strongly suggests that hot-carrier-induced desorption occurs at the Pd island surface. When acetylene is present along with hydrogen, the selectivity for photocatalytic ethylene production relative to ethane is strongly enhanced, approaching 40:1. These observations indicate that antenna−reactor complexes may greatly expand possibilities for developing designer photocatalytic substrates.
Nature Communications | 2015
Christoph Baeumer; Diomedes Saldana-Greco; John Mark P. Martirez; Andrew M. Rappe; Moonsub Shim; Lane W. Martin
The next technological leap forward will be enabled by new materials and inventive means of manipulating them. Among the array of candidate materials, graphene has garnered much attention; however, due to the absence of a semiconducting gap, the realization of graphene-based devices often requires complex processing and design. Spatially controlled local potentials, for example, achieved through lithographically defined split-gate configurations, present a possible route to take advantage of this exciting two-dimensional material. Here we demonstrate carrier density modulation in graphene through coupling to an adjacent ferroelectric polarization to create spatially defined potential steps at 180°-domain walls rather than fabrication of local gate electrodes. Periodic arrays of p-i junctions are demonstrated in air (gate tunable to p-n junctions) and density functional theory reveals that the origin of the potential steps is a complex interplay between polarization, chemistry, and defect structures in the graphene/ferroelectric couple.
Journal of the American Chemical Society | 2015
John Mark P. Martirez; Seungchul Kim; Erie H. Morales; Benjamin T. Diroll; Matteo Cargnello; Thomas R. Gordon; Christopher B. Murray; Dawn A. Bonnell; Andrew M. Rappe
In addition to composition, the structure of a catalyst is another fundamental determinant of its catalytic reactivity. Recently, anomalous Ti oxide-rich surface phases of ternary oxides have been stabilized as nonstoichiometric epitaxial overlayers. These structures give rise to different modes of oxygen binding, which may lead to different oxidative chemistry. Through density functional theory investigations and electrochemical measurements, we predict and subsequently show that such a TiO2 double-layer surface reconstruction enhances the oxygen evolving activity of the perovskite-type oxide SrTiO3. Our theoretical work suggests that the improved activity of the restructured TiO2(001) surface toward oxygen formation stems from (i) having two Ti sites with distinct oxidation activity and (ii) being able to form a strong O-O moiety (which reduces overbonding at Ti sites), which is a direct consequence of (iii) having a labile lattice O that is able to directly participate in the reaction. Here, we demonstrate the improvement of the catalytic performance of a well-known and well-studied oxide catalyst through more modern methods of materials processing, predicted through first-principles theoretical modeling.
Nano Letters | 2014
Wissam A. Saidi; John Mark P. Martirez; Andrew M. Rappe
We present a systematic evaluation of the effects of polarization switchability on surface structure and stoichiometry in BaTiO3 and PbTiO3 ferroelectric oxides. We show that charge passivation, mostly by ionic surface reconstructions, is the driving force for the stability of the surfaces, which suggests that varying the substrate polarization offers a new mechanism for controlling surface reconstructions in polar systems and inducing highly nonstoichiometric structures. Conversely, for thin-films the chemical environment can drive polarization switching via induced compositional changes on the surface. We find that the value of the oxygen partial pressure for the positive-to-negative polar transition is in good agreement with the recent experimental value for thin-film PbTiO3. For BaTiO3, we show that it is harder for oxygen control to drive polar transition because it is more difficult to reduce. This study opens up the possibility of real-time control of structure and composition of oxide surfaces.
ACS Nano | 2016
John Mark P. Martirez; Emily A. Carter
The Haber-Bosch process for NH3 synthesis is arguably one of the greatest inventions of the 20th century, with a massive footprint in agriculture and, historically, warfare. Current catalysts for this reaction use Fe for N2 activation, conducted at high temperatures and pressures to improve conversion rate and efficiency. A recent finding shows that plasmonic metal nanoparticles can either generate highly reactive electrons and holes or induce resonant surface excitations through plasmonic decay, which catalyze dissociation and redox reactions under mild conditions. It is therefore appealing to consider AuM (M = Fe, Co, Ni, and Mo) alloys to combine the strongly plasmonic nature of Au and the catalytic nature of M metals toward N2 dissociation, which together might facilitate ammonia production. To this end, through density functional theory, we (i) explore the feasibility of forming these surface alloys, (ii) find a pathway that may stabilize/deactivate surface M substituents during fabrication, and (iii) define a complementary route to reactivate them under operational conditions. Finally, we evaluate their reactivity toward N2, as well as their ability to support a pathway for N2 dissociation with a low thermodynamic barrier. We find that AuFe possesses similar appealing qualities, including relative stability with respect to phase separation, reversibility of Fe oxidation and reduction, and reactivity toward N2. While AuMo achieves the best affinity toward N2, its strong propensity toward oxidation could greatly limit its use.
Journal of the American Chemical Society | 2017
John Mark P. Martirez; Emily A. Carter
Localized surface plasmon resonances (LSPRs) offer the possibility of light-activated chemical catalysis on surfaces of strongly plasmonic metal nanoparticles. This technology relies on lower-barrier bond formation and/or dissociation routes made available through energy transfer following the eventual decay of LSPRs. The coupling between these decay processes and a chemical trajectory (nuclear motion, charge-transfer, intersystem crossing, etc.) dictates the availability of these alternative (possibly lower barrier) excited-state channels. The Haber-Bosch method of NH3 synthesis from N2 and H2 is notoriously energy intensive. This is due to the difficulty of N2 dissociation despite the overall reaction being thermodynamically favorable at ambient temperatures and pressures. LSPRs may provide means to improve the kinetics of N2 dissociation via induced resonance electronic excitation. In this work, we calculate, via embedded n-electron valence second-order perturbation theory within the density functional embedding theory, the excited-state potential energy surfaces for dissociation of N2 on an Fe-doped Au(111) surface. This metal alloy may take advantage simultaneously of the strong LSPR of Au and the catalytic activity of Fe toward N2 dissociation. We find the ground-state dissociation activation energy to be 4.74 eV/N2, with Fe as the active site on the surface. Consecutive resonance energy transfers (RETs) may be accessed due to the availability of many electronically excited states with intermediate energies arising from the metal surface that may couple to states induced by the Fe-dopant and the adsorbate molecule, and crossing between excited states may effectively lower the dissociation barrier to 1.33 eV. Our work illustrates that large energetic barriers, prohibitive toward chemical reaction, may be overcome through multiple RETs facilitating an otherwise difficult chemical process.
ACS Nano | 2014
Erie Morales; John Mark P. Martirez; Wissam A. Saidi; Andrew M. Rappe; Dawn A. Bonnell
Coexistence of surface reconstructions is important due to the diversity in kinetic and thermodynamic processes involved. We identify the coexistence of kinetically accessible phases that are chemically identical and form coherent interfaces. Here, we establish the coexistence of two phases, c(2 × 2) and c(4 × 4), in BaTiO3(001) with atomically resolved Scanning Tunneling Microscopy (STM). First-principles thermodynamic calculations determine that TiO adunits and clusters compose the surfaces. We show that TiO diffusion results in a kinetically accessible c(2 × 2) phase, while TiO clustering results in a kinetically and thermodynamically stable c(4 × 4) phase. We explain the formation of domains based on the diffusion of TiO units. The diffusion direction determines the observed 1D coherent interfaces between c(2 × 2) and c(4 × 4) reconstructions. We propose atomic models for the c(2 × 2), c(4 × 4), and 1D interfaces.
Journal of Physical Chemistry Letters | 2014
Nathan Z. Koocher; John Mark P. Martirez; Andrew M. Rappe
Highly reduced surface reconstructions of BaTiO3 (001) have been found to be composed of a TiO2 surface covered with Ti adatoms occupying surface interstitial sites. We predict the reactivity of these highly oxophilic and reduced surface Ti species through density functional theory, where we calculate the adsorption of H2O on the (√5 × √5)R26.6° TiO2-Ti3/5 reconstruction. H2O serves as the primary O source and oxidizing agent. We demonstrate that H2O oxidizes some of the Ti adatoms, shifting their occupied 3d states to the surface conduction band edge. We find that, due to the high concentration of reduced Ti species on the surface, a dissociative adsorption of water on the reconstructed surface can also lead to the formation of surface hydrides, which serve as a precursor for H2 evolution. This suggests that the reconstructed surface may be an attractive single-phase hydrogen evolution catalyst.
Science Advances | 2017
John Mark P. Martirez; Emily A. Carter
We propose a promising new method of solar-driven ammonia synthesis with metal nanoparticles. Despite more than a century of advances in catalyst and production plant design, the Haber-Bosch process for industrial ammonia (NH3) synthesis still requires energy-intensive high temperatures and pressures. We propose taking advantage of sunlight conversion into surface plasmon resonances in Au nanoparticles to enhance the rate of the N2 dissociation reaction, which is the bottleneck in NH3 production. We predict that this can be achieved through Mo doping of the Au surface based on embedded multireference correlated wave function calculations. The Au component serves as a light-harvesting antenna funneling energy onto the Mo active site, whereby excited-state channels (requiring 1.4 to 1.45 eV, near-infrared–to–visible plasmon resonances) may be accessed. This effectively lowers the energy barriers to 0.44 to 0.77 eV/N2 (43 to 74 kJ/mol N2) from 3.5 eV/N2 (335 kJ/mol N2) in the ground state. The overall process requires three successive surface excitation events, which could be facilitated by amplified resonance energy transfer due to plasmon local field enhancement.
Journal of the American Chemical Society | 2018
Robert B. Wexler; John Mark P. Martirez; Andrew M. Rappe
The activity of Ni2P catalysts for the hydrogen evolution reaction (HER) is currently limited by strong H adsorption at the Ni3-hollow site. We investigate the effect of surface nonmetal doping on the HER activity of the Ni3P2 termination of Ni2P(0001), which is stable at modest electrochemical conditions. Using density functional theory (DFT) calculations, we find that both 2 p nonmetals and heavier chalcogens provide nearly thermoneutral H adsorption at moderate surface doping concentrations. We also find, however, that only chalcogen substitution for surface P is exergonic. For intermediate surface concentrations of S, the free energy of H adsorption at the Ni3-hollow site is -0.11 eV, which is significantly more thermoneutral than the undoped surface (-0.45 eV). We use the regularized random forest machine learning algorithm to discover the relative importance of structure and charge descriptors, extracted from the DFT calculations, in determining the HER activity of Ni2P(0001) under different doping concentrations. We discover that the Ni-Ni bond length is the most important descriptor of HER activity, which suggests that the nonmetal dopants induce a chemical pressure-like effect on the Ni3-hollow site, changing its reactivity through compression and expansion.