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This work presents a novel, to the best of our knowledge, cross correlation technique for determining the laser heating-induced Raman shift laser power coefficientψrequired for energy transport state-resolved Raman (ET-Raman) methods. The cross correlation method determines the measure of similarity between the experimental intensity data and a varying test Gaussian signal. By circumventing the errors inherent in any curve fittings, the cross correlation method quickly and accurately determines the location where the test Gaussian signal peak is most like the Raman peak, thereby revealing the peak location and ultimately the value ofψ. This method improves the reliability of optothermal Raman-based methods for micro/nanoscale thermal measurements and offers a robust approach to data processing through a global treatment of Raman spectra. 

In the last two decades, tremendous research has been conducted on the discovery, design and synthesis, characterization, and applications of two-dimensional (2D) materials. Thermal conductivity and interface thermal conductance/resistance of 2D materials are two critical properties in their applications. Raman spectroscopy, which measures the inelastic scattering of photons by optical phonons, can distinct a 2D material's temperature from its surrounding materials', featuring unprecedented spatial resolution (down to the atomic level). Raman-based thermometry has been used tremendously for characterizing the thermal conductivity of 2D materials (suspended or supported) and interface thermal conductance/resistance. Very large data deviations have been observed in literature, partly due to physical phenomena and factors not considered in measurements. Here, we provide a critical review, analysis, and perspectives about a broad spectrum of physical problems faced in Raman-based thermal characterization of 2D materials, namely interface separation, localized stress due to thermal expansion mismatch, optical interference, conjugated phonon, and hot carrier transport, optical–acoustic phonon thermal nonequilibrium, and radiative electron–hole recombination in monolayer 2D materials. Neglect of these problems will lead to a physically unreasonable understanding of phonon transport and interface energy coupling. In-depth discussions are also provided on the energy transport state-resolved Raman (ET-Raman) technique to overcome these problems and on future research challenges and needs. 

Abstract Balancing kinetics, a crucial priority in catalysis, is frequently achieved by sacrificing activity of elementary steps to suppress side reactions and enhance catalyst stability. Dry reforming of methane (DRM), a process operated at high temperature, usually involves fast C-H activation but sluggish carbon removal, resulting in coke deposition and catalyst deactivation. Studies focused solely on catalyst innovation are insufficient in addressing coke formation efficiently. Herein, we develop coke-free catalysts that balance kinetics of elementary steps for overall thermodynamics optimization. Beginning from a highly active cobalt aluminum oxide (CoAl₂O₄) catalyst that is susceptible to severe coke formation, we substitute aluminum (Al) with gallium (Ga), reporting a CoAl_0.5Ga_1.5O₄-R catalyst that performs DRM stably over 1000 hours without observable coke deposition. We find that Ga enhances DRM stability by suppressing C-H activation to balance carbon removal. A series of coke-free DRM catalysts are developed herein by partially substituting Al from CoAl₂O₄with other metals. 

Abstract Raman spectroscopy-based temperature sensing usually tracks the change of Raman wavenumber, linewidth and intensity, and has found very broad applications in characterizing the energy and charge transport in nanomaterials over the last decade. The temperature coefficients of these Raman properties are highly material-dependent, and are subjected to local optical scattering influence. As a result, Raman-based temperature sensing usually suffers quite large uncertainties and has low sensitivity. Here, a novel method based on dual resonance Raman phenomenon is developed to precisely measure the absolute temperature rise of nanomaterial (nm WS 2 film in this work) from 170 to 470 K. A 532 nm laser (2.33 eV photon energy) is used to conduct the Raman experiment. Its photon energy is very close to the excitonic transition energy of WS 2 at temperatures close to room temperature. A parameter, termed resonance Raman ratio (R3) Ω = I A 1g / I E 2g is introduced to combine the temperature effects on resonance Raman scattering for the A 1g and E 2g modes. Ω has a change of more than two orders of magnitude from 177 to 477 K, and such change is independent of film thickness and local optical scattering. It is shown that when Ω is varied by 1%, the temperature probing sensitivity is 0.42 K and 1.16 K at low and high temperatures, respectively. Based on Ω, the in-plane thermal conductivity ( k ) of a ∼25 nm-thick suspended WS 2 film is measured using our energy transport state-resolved Raman (ET-Raman). k is found decreasing from 50.0 to 20.0 Wm −1 K −1 when temperature increases from 170 to 470 K. This agrees with previous experimental and theoretical results and the measurement data using our FET-Raman. The R3 technique provides a very robust and high-sensitivity method for temperature probing of nanomaterials and will have broad applications in nanoscale thermal transport characterization, non-destructive evaluation, and manufacturing monitoring.