Photothermal nonlinearity in plasmon-assisted photocatalysis.

Understanding the intricate relationship between illumination and temperature in metallic nano-particles is crucial for elucidating the role of illumination in various physical processes which rely on plasmonic enhancement but are also sensitive to temperature. Recent studies have shown that the temperature rise in optically thick ensembles of metal nanoparticles under intense illumination is dominated by the thermal conductivity of the host, rather than by the optical properties of the metal or the host. Here, we show that the temperature dependence of the thermal conductivity of the host dominates the nonlinear photothermal response of these systems. In particular, this dependence typically causes the temperature rise to become strongly sublinear, reaching even several tens of percent. We then show that this effect can explain experimental observations in several recent plasmon-assisted photocatalysis experiments. Under certain conditions, we show that thermal emission may also contribute to photothermal nonlinearity. This shows that any claim for the dominance of non-thermal electrons in plasmon-assisted photocatalysis must account first for this photothermal nonlinear mechanism.

[1]  Ieng-Wai Un,et al.  Matters Arising in --"Plasmon-driven carbon-fluorine (C(sp^$3$)-F) bond activation with mechanistic insights into hot-carrier-mediated pathways" , 2021, 2105.06382.

[2]  Ieng-Wai Un,et al.  The Role of Heat Generation and Fluid Flow in Plasmon-Enhanced Reduction–Oxidation Reactions , 2021, ACS Photonics.

[3]  Hui Wang,et al.  Plasmon-driven photocatalytic molecular transformations on metallic nanostructure surfaces: mechanistic insights gained from plasmon-enhanced Raman spectroscopy , 2021 .

[4]  Y. Sivan,et al.  Recent developments in plasmon-assisted photocatalysis—A personal Perspective , 2020, 2009.00286.

[5]  Yonatan Sivan,et al.  Parametric study of temperature distribution in plasmon-assisted photocatalysis. , 2020, Nanoscale.

[6]  Ieng-Wai Un,et al.  Thermo-optic nonlinearity of single metal nanoparticles under intense continuous wave illumination , 2020, 2006.11884.

[7]  V. Shalaev,et al.  Plasmonic Photosensitizers: TiN@TiO 2 Core–Shell Nanoparticles as Plasmon‐Enhanced Photosensitizers: The Role of Hot Electron Injection (Laser Photonics Rev. 14(5)/2020) , 2020 .

[8]  V. Shalaev,et al.  TiN@TiO2 Core–Shell Nanoparticles as Plasmon‐Enhanced Photosensitizers: The Role of Hot Electron Injection , 2020, Laser & Photonics Reviews.

[9]  Y. Sivan,et al.  Experimental practices required to isolate thermal effects in plasmonic photo-catalysis: lessons from recent experiments , 2020 .

[10]  A. Baldi,et al.  Simple experimental procedures to discern photothermal processes in plasmon-driven chemistry , 2020, 2001.08402.

[11]  Yonatan Dubi,et al.  Thermal effects – an alternative mechanism for plasmon-assisted photocatalysis , 2019, Chemical science.

[12]  Ieng-Wai Un,et al.  Size-dependence of the photothermal response of a single metal nanosphere , 2019, Journal of Applied Physics.

[13]  Jie Liu,et al.  Confirming nonthermal plasmonic effects enhance CO2 methanation on Rh/TiO2 catalysts , 2019, Nano Research.

[14]  S. Reich,et al.  Theory of hot electrons: general discussion. , 2019, Faraday discussions.

[15]  Ieng-Wai Un,et al.  Comment on “Quantifying hot carrier and thermal contributions in plasmonic photocatalysis” , 2019, Science.

[16]  S. Maier,et al.  Spectral Screening of the Energy of Hot Holes over a Particle Plasmon Resonance. , 2019, Nano letters.

[17]  Jie Liu,et al.  Light-Induced Thermal Gradients in Ruthenium Catalysts Significantly Enhance Ammonia Production. , 2019, Nano letters.

[18]  Y. Sivan,et al.  “Hot” electrons in metallic nanostructures—non-thermal carriers or heating? , 2018, Light: Science & Applications.

[19]  N. V. van Hulst,et al.  Tracking ultrafast hot-electron diffusion in space and time by ultrafast thermomodulation microscopy , 2018, Science Advances.

[20]  Hangqi Zhao,et al.  Quantifying hot carrier and thermal contributions in plasmonic photocatalysis , 2018, Science.

[21]  H. Clercx,et al.  Quantifying Photothermal and Hot Charge Carrier Effects in Plasmon-Driven Nanoparticle Syntheses. , 2018, ACS nano.

[22]  J. Beuth,et al.  Thermal conductivity of metal powders for powder bed additive manufacturing , 2018 .

[23]  Weitao Yang,et al.  Plasmon-Enhanced Catalysis: Distinguishing Thermal and Nonthermal Effects. , 2018, Nano letters.

[24]  A. Kildishev,et al.  Temperature-Dependent Optical Properties of Single Crystalline and Polycrystalline Silver Thin Films , 2017 .

[25]  J. Valentine,et al.  Harvesting the loss: surface plasmon-based hot electron photodetection , 2017 .

[26]  S. Hashimoto,et al.  Plasmonic-heating-induced nanofabrication on glass substrates. , 2016, Nanoscale.

[27]  Y. Sivan,et al.  Nonlinear plasmonics at high temperatures , 2016, 1607.03481.

[28]  Cheng‐Wei Lin,et al.  Temperature- and roughness- dependent permittivity of annealed/unannealed gold films. , 2016, Optics express.

[29]  Romain Quidant,et al.  Fast and Transparent Adaptive Lens Based on Plasmonic Heating , 2015 .

[30]  Tomasz S. Wiśniewski,et al.  A review of models for effective thermal conductivity of composite materials , 2014 .

[31]  A. Crut,et al.  Advances in femto-nano-optics: ultrafast nonlinearity of metal nanoparticles , 2014 .

[32]  R. Boyd,et al.  The third-order nonlinear optical susceptibility of gold , 2014 .

[33]  Romain Quidant,et al.  Nanoplasmonics for chemistry. , 2014, Chemical Society reviews.

[34]  C. Clavero,et al.  Plasmon-induced hot-electron generation at nanoparticle/metal-oxide interfaces for photovoltaic and photocatalytic devices , 2014, Nature Photonics.

[35]  Anne M. Hofmeister,et al.  Thermal diffusivity and thermal conductivity of single-crystal MgO and Al2O3 and related compounds as a function of temperature , 2014, Physics and Chemistry of Minerals.

[36]  P. Nordlander,et al.  Hot-electron-induced dissociation of H2 on gold nanoparticles supported on SiO2. , 2014, Journal of the American Chemical Society.

[37]  Satoshi Kawata,et al.  Measurement of a saturated emission of optical radiation from gold nanoparticles: application to an ultrahigh resolution microscope. , 2014, Physical review letters.

[38]  J. Khurgin,et al.  Plasmonic enhancement of the third order nonlinear optical phenomena: figures of merit. , 2013, Optics express.

[39]  M. Fox.  The Handbook on Optical Constants of Metals: In Tables and Figures & The Handbook on Optical Constants of Semiconductors: In Tables and Figures, by Sadao Adachi , 2013 .

[40]  Florian Libisch,et al.  Hot electrons do the impossible: plasmon-induced dissociation of H2 on Au. , 2013, Nano letters.

[41]  H. Xin,et al.  Singular characteristics and unique chemical bond activation mechanisms of photocatalytic reactions on plasmonic nanostructures. , 2012, Nature materials.

[42]  G. Volpe,et al.  Near-field mapping of plasmonic antennas by multiphoton absorption in poly(methyl methacrylate). , 2012, Nano letters.

[43]  S. Linic,et al.  Plasmonic-metal nanostructures for efficient conversion of solar to chemical energy. , 2011, Nature materials.

[44]  F. D. Abajo,et al.  Spatial Nonlocality in the Optical Response of Metal Nanoparticles , 2011 .

[45]  Romain Quidant,et al.  Plasmon-assisted optofluidics. , 2011, ACS nano.

[46]  G. Baffou,et al.  Plasmon-Assisted Opto! uidics , 2011 .

[47]  Jean-Marc Franssen,et al.  Fire design of steel structures , 2010 .

[48]  Romain Quidant,et al.  Nanoscale control of optical heating in complex plasmonic systems. , 2010, ACS nano.

[49]  R. Shimizu,et al.  Near-infrared continuous-wave light driving a two-photon photochromic reaction with the assistance of localized surface plasmon. , 2009, Journal of the American Chemical Society.

[50]  Andrey V. Gusarov,et al.  Model of thermal conductivity in powder beds , 2009 .

[51]  Jun Wang,et al.  Inorganic and hybrid nanostructures for optical limiting , 2009 .

[52]  H. Misawa,et al.  Nanoparticle plasmon-assisted two-photon polymerization induced by incoherent excitation source. , 2008, Journal of the American Chemical Society.

[53]  F. D. Abajo,et al.  Nonlocal Effects in the Plasmons of Strongly Interacting Nanoparticles, Dimers, and Waveguides , 2008, 0802.0040.

[54]  B. Palpant,et al.  Counterintuitive thermo-optical response of metal-dielectric nanocomposite materials as a result of local electromagnetic field enhancement , 2006 .

[55]  Louis E. Brus,et al.  Silver Nanodisk Growth by Surface Plasmon Enhanced Photoreduction of Adsorbed [Ag+] , 2003 .

[56]  C. Mirkin,et al.  Photoinduced Conversion of Silver Nanospheres to Nanoprisms , 2001, Science.

[57]  Don A. Gregory,et al.  Cancellation of photoinduced absorption in metal nanoparticle composites through a counterintuitive consequence of local field effects , 1997 .

[58]  Z. Kam,et al.  Absorption and Scattering of Light by Small Particles , 1998 .

[59]  Richard M. Osgood,et al.  Direct Observation of the Local-Field-Enhanced Surface Photochemical Reactions , 1983 .

[60]  A. Nitzan,et al.  Theoretical model for enhanced photochemistry on rough surfaces , 1981 .

[61]  S. Saxena,et al.  THERMAL CONDUCTIVITY OF GASEOUS AMMONIA IN THE TEMPERATURE RANGE 358-925 K. , 1981 .

[62]  S. Saxena,et al.  Thermal conductivity of nitrogen in the temperature range 350–2500 K , 1975 .

[63]  R. W. Christy,et al.  Optical constants of copper and nickel as a function of temperature , 1975 .

[64]  F. W. Sears,et al.  Thermodynamics, kinetic theory, and statistical thermodynamics , 1975 .

[65]  D. Whiffen.  Thermodynamics , 1973, Nature.

[66]  G. P. Pells,et al.  The optical properties of copper and gold as a function of temperature , 1969 .