Remote near-field spectroscopy of vibrational strong coupling between organic molecules and phononic nanoresonators

Vibrational strong coupling (VSC) promises ultrasensitive IR spectroscopy and modification of material properties. Here, nanoscale mapping of VSC between organic molecules and individual IR nanoresonators is achieved by remote near-field spectroscopy. Phonon polariton (PhP) nanoresonators can dramatically enhance the coupling of molecular vibrations and infrared light, enabling ultrasensitive spectroscopies and strong coupling with minute amounts of matter. So far, this coupling and the resulting localized hybrid polariton modes have been studied only by far-field spectroscopy, preventing access to modal near-field patterns and dark modes, which could further our fundamental understanding of nanoscale vibrational strong coupling (VSC). Here we use infrared near-field spectroscopy to study the coupling between the localized modes of PhP nanoresonators made of h-BN and molecular vibrations. For a most direct probing of the resonator-molecule coupling, we avoid the direct near-field interaction between tip and molecules by probing the molecule-free part of partially molecule-covered nanoresonators, which we refer to as remote near-field probing. We obtain spatially and spectrally resolved maps of the hybrid polariton modes, as well as the corresponding coupling strengths, demonstrating VSC on a single PhP nanoresonator level. Our work paves the way for near-field spectroscopy of VSC phenomena not accessible by conventional techniques.This work was supported by the MCIN/AEI/10.13039/501100011033 under the María de Maeztu Units of Excellence Program (CEX2020-001038-M) and the Projects RTI2018-094830-B-100, PID2021-123949OB-I00, PID2019-107432GB-I00 and PID2021-122511OB-I00, as well as by the Graphene Flagship (GrapheneCore3, No. 881603). J.L. and J.H.E. are grateful for support from the Office of Naval Research (Award No. N00014-20-1-2474), for the BN crystal growth. S.V. acknowledges financial support by the Comunidad de Madrid through the Atracción de Talento program (grant no. 2020-T1/IND-20041). C.M.-E., R.E., and J.A. received funding from grant no. IT 1526-22 from the Basque Government for consolidated groups of the Basque University

Real-space observation of ultraconfined in-plane anisotropic acoustic terahertz plasmon polaritons

Thin layers of in-plane anisotropic materials can support ultraconfined polaritons, whose wavelengths depend on the propagation direction. Such polaritons hold potential for the exploration of fundamental material properties and the development of novel nanophotonic devices. However, the real-space observation of ultraconfined in-plane anisotropic plasmon polaritons (PPs)-which exist in much broader spectral ranges than phonon polaritons-has been elusive. Here we apply terahertz nanoscopy to image in-plane anisotropic low-energy PPs in monoclinic Ag2Te platelets. The hybridization of the PPs with their mirror image-by placing the platelets above a Au layer-increases the direction-dependent relative polariton propagation length and the directional polariton confinement. This allows for verifying a linear dispersion and elliptical isofrequency contour in momentum space, revealing in-plane anisotropic acoustic terahertz PPs. Our work shows high-symmetry (elliptical) polaritons on low-symmetry (monoclinic) crystals and demonstrates the use of terahertz PPs for local measurements of anisotropic charge carrier masses and damping.The work was financially supported by the Spanish Ministry of Science and Innovation under the María de Maeztu Units of Excellence Program (CEX2020-001038-M/MCIN/AEI/10.13039/501100011033) (R.H., A.C., L.E.H. and E.A.); Projects PID2021-123949OB-I00 (R.H.), PID2019-109905GB-C21 (M.G.V. and I.E.), RTI2018-094861-B-100 (L.E.H.), PID2019-107432GB-I00 (J.A.) and PID2019-107338RB-C61 (E.A.) funded by MCIN/AEI/10.13039/501100011033 and by ‘ERDF—A Way of Making Europe’; the National Natural Science Foundation of China (NSFC) (52225207 and 11934005) and the Shanghai Pilot Program for Basic Research—Fudan University 21TQ1400100 (21TQ006) (F.X.X.); NSFC grant no. 61988102 and the Science and Technology Commission of Shanghai Municipality (nos. 23010503400 and 23ZR1443500) (S.C.); the Czech Science Foundation GACR under the Junior Star grant no. 23-05119M (A.K.); the European Research Council (ERC) under grant agreement no. 101020833 (M.G.V.); the German Research Foundation (DFG) under project nos. 467576442 (I.N.) and GA 3314/1-1–FOR 5249 (QUAST) (M.G.V.); the Gipuzkoa Council (Spain) in the frame of the Gipuzkoa Fellows Program (B.M.-G.); and the University groups of the Basque Government (IT1526-22) (J.A.).Peer reviewe

An Emerging Nanozyme Class for à la carte Enzymatic-Like Activities based on Protein-Metal Nanocluster Hybrids

In this study, the goal is to fabricate robust and highly efficient peroxidase-like nanozymes that can ultimately be assembled into films for their easy reuse in catalytic cycles. Nanozymes are designed by mimicking the strategy adopted by metalloproteins to accommodate metal cofactors within their protein structure. The engineered consensus tetratricopeptide repeat (CTPR) protein module is selected as the scaffold to guide the growth and the stabilization of a library of in situ synthesized metal nanoclusters. A deep investigation of the interplay between the composition and function of the nanozymes reveals the impact of the protein templates and nanocluster composition on the peroxidase-like activity of the hybrids. Moreover, among a total of 24 hybrids, a top-performing nanozyme results from the growth of Au/Pt bimetallic nanoclusters on a CTPR protein with engineered histidine coordination sites. These nanozymes exhibit improved thermostability and resistance to hydrogen peroxide compared to natural peroxidases like horseradish peroxidase. Finally, it shows the easy fabrication of nanozyme composite films guided throughout the intrinsic self-assembling properties of the CTPR scaffold. These heterogeneous solid materials are reused in several reaction cycles without significant loss of the catalytic performance, proving these protein-templated nanozymes as an advantageous alternative to natural enzymes.The authors thank Gabriela Guedes, Andoni Rodriguez, and Alessandro Silvestri for their inestimable help in the characterization of the nanozymes. The authors thank Dr. D. di Silvio at CIC biomaGUNE for support with the acquisition and analysis of XPS data. A.L.C. acknowledges support by the Agencia Estatal de Investigación Grants: PID2019-111649RB-I00 funded by MCIN/AEI/ 10.13039/501100011033 and Grant PDC2021-120957-I00 funded by MCIN/AEI/ 10.13039/501100011033 and by the “European Union NextGenerationEU/PRTR”. A.L.C. acknowledges support by the European Research Council Grants: ERC-CoG-648071-ProNANO and ERC-PoC-841063- NIMM. This work was performed under the Maria de Maeztu Units of Excellence Program from Q5 the Spanish State Research Agency grant no. MDM-2017-0720. A.B. gratefully acknowledges the financial support from the Spanish Research Agency (AEI) for the financial support (PID2019-110239RB-I00 funded by MCIN/AEI/10.13039/501100011033/ and by the “European Union NextGenerationEU/PRTR”; RYC2018-025923-I from RyC program – MCIN/AEI/10.13039/501100011033 and FSE “invierte en tu futuro”), BBVA Foundation – IN[21]_CBB_QUI_0086, and UPV/EHU- GIU21-033)

Quantification of reagent mixing in liquid flow cells for Liquid Phase-TEM

Liquid-Phase Transmission Electron Microscopy (LP-TEM) offers the opportunity to study nanoscale dynamics of phenomena related to materials and life science in a native liquid environment and in real time. Until now, the opportunity to control/induce such dynamics by changing the chemical environment in the liquid flow cell (LFC) has rarely been exploited due to an incomplete understanding of hydrodynamic properties of LP-TEM flow systems. This manuscript introduces a method for hydrodynamic characterization of LP-TEM flow systems based on monitoring transmitted intensity while flowing a strongly electron scattering contrast agent solution. Key characteristic temporal indicators of solution replacement for various channel geometries were experimentally measured. A numerical physical model of solute transport based on realistic flow channel geometries was successfully implemented and validated against experiments. The model confirmed the impact of flow channel geometry on the importance of convective and diffusive solute transport, deduced by experiment, and could further extend understanding of hydrodynamics in LP-TEM flow systems. We emphasize that our approach can be applied to hydrodynamic characterization of any customized LP-TEM flow system. We foresee the implemented predictive model driving the future design of application-specific LP-TEM flow systems and, when combined with existing chemical reaction models, to a flourishing of the planning and interpretation of experimental observations.This work was supported by the Basque Government (PIBA 2018–34, RIS3 2018222034) and Diputacion Foral de Gipuzkoa (RED2018, RED2019). We acknowledge support by Spanish MINECO under the Maria de Maeztu Units of Excellence Program (MDM-2016–0618). S. M. acknowledges funding from the Basque Ministry of Education in the frame of the “Programa Predoctoral de Formación de Personal Investigador no Doctor” (grant reference: PRE_2019_1_0239).Peer reviewe

Hydrogen Production from Formic Acid over Au Catalysts Supported on Carbon: Comparison with Au Catalysts Supported on SiO₂ and Al₂O₃

Characteristics and catalytic activity in hydrogen production from formic acid of Au catalysts supported on porous N-free (Au/C) and N-doped carbon (Au/N-C) have been compared with those of Au/SiO2 and Au/Al2O3 catalysts. Among the catalysts examined, the Au/N-C catalyst showed the highest Au mass-based catalytic activity. The following trend was found at 448 K: Au/N-C > Au/SiO2 > Au/Al2O3, Au/C. The trend for the selectivity in hydrogen production was different: Au/C (99.5%) > Au/Al2O3 (98.0%) > Au/N-C (96.3%) > Au/SiO2 (83.0%). According to XPS data the Au was present in metallic state in all catalysts after the reaction. TEM analysis revealed that the use of the N-C support allowed obtaining highly dispersed Au nanoparticles with a mean size of about 2 nm, which was close to those for the Au catalysts on the oxide supports. However, it was by a factor of 5 smaller than that for the Au/C catalyst. The difference in dispersion could explain the difference in the catalytic activity for the carbon-based catalysts. Additionally, the high activity of the Au/N-C catalyst could be related to the presence of pyridinic type nitrogen on the N-doped carbon surface, which activates the formic acid molecule forming pyridinium formate species further interacting with Au. This was confirmed by density functional theory (DFT) calculations. The results of this study may assist the development of novel Au catalysts for different catalytic reactions