Interfacial electric fields play crucial roles in electrochemistry, catalysis, and solar energy conversion. Understanding of the interfacial electric field effects has been hindered by the lack of a direct spectroscopic method to probe of the interfacial field at the molecular level. Here, we report the characterization of the field and interfacial structure at Au/diisocyanide/aqueous electrolyte interfaces, using a combination of in situ electrochemical vibrational sum frequency generation (SFG) spectroscopy, density functional theory (DFT) calculations, and molecular dynamics (MD) simulations. For 1,4-phenylene diisocyanide (PDI), 4,4′-biphenyl diisocyanide (BPDI), and 4,4″-p-terphenyl diisocyanide (TPDI), our results reveal that the frequency of the gold-bound NC stretch mode of the diisocyanide self-assembled monolayer (SAM) increases linearly with the applied potential, suggesting that SFG can be an in situ probe of the strength of the electric field at electrode/electrolyte interfaces. Using DFT-computed Stark tuning rates of model complexes, the electric field strength at the metal/SAM/electrolyte interfaces is estimated to be 108–109 V/m. The linear dependence of the vibrational frequency (and field) with applied potential is consistent with an electrochemical double-layer structure that consists of a Helmholtz layer in contact with a diffused layer. The Helmholtz layer thickness is approximately the same as the molecular length for PDI, suggesting a well-ordered SAM with negligible electrolyte penetration. For BPDI and TPDI, we found that the Helmholtz layer is thinner than the monolayer of molecular adsorbates, indicating that the electrolyte percolates into the SAM, as shown by molecular dynamics simulations of the Au/PDI/electrolyte interface. The reported analysis demonstrates that a combination of in situ SFG probes and computational modeling provides a powerful approach to elucidate the structure of electrochemical interfaces at the detailed molecular level.

Attaching molecular catalysts to metal and semiconductor electrodes is a promising approach to developing new catalytic electrodes with combined advantages of molecular and heterogeneous catalysts. However, the effect of the interfacial electric field on the stability, activity, and selectivity of the catalysts is often poorly understood due to the complexity of interfaces. In this work, we examine the strength of the interfacial field at the binding site of CO 2 reduction catalysts including Re(S-2,2′-bipyridine)(CO) 3 Cl and Mn(S-2,2′-bipyridine)(CO) 3 Br immobilized on Au electrodes. The vibrational spectra are probed by sum frequency generation spectroscopy (SFG), showing pronounced potential-dependent frequency shifts of the carbonyl stretching modes. Calculations of SFG spectra and Stark tuning rates based on density functional theory allow for direct interpretation of the configurations of the catalysts bound to the surfaces and the influence of the interfacial electric field. We find that electrocatalysts supported on Au electrodes have tilt angles of about 65−75°relative to the surface normal with one of the carbonyl ligands in direct contact with the surface. Large interfacial electric fields of 10 8 −10 9 V/m are determined through the analysis of experimental frequency shifts and theoretical Stark tuning rates of the symmetric CO stretching mode. These large electric fields thus significantly influence the CO 2 binding site.

The naturally microstructure-bioinspired piezoresistive sensor for human–machine interaction and human health monitoring represents an attractive opportunity for wearable bioelectronics. However, due to the trade-off between sensitivity and linear detection range, obtaining piezoresistive sensors with both a wide pressure monitoring range and a high sensitivity is still a great challenge. Herein, we design a hierarchically microstructure-bioinspired flexible piezoresistive sensor consisting of a hierarchical polyaniline/polyvinylidene fluoride nanofiber (HPPNF) film sandwiched between two interlocking electrodes with microdome structure. Ascribed to the substantially enlarged 3D deformation rates, these bioelectronics exhibit an ultrahigh sensitivity of 53 kPa–1, a pressure detection range from 58.4 to 960 Pa, a fast response time of 38 ms, and excellent cycle stability over 50 000 cycles. Furthermore, this conformally skin-adhered sensor successfully demonstrates the monitoring of human physiological signals and movement states, such as wrist pulse, throat activity, spinal posture, and gait recognition. Evidently, this hierarchically microstructure-bioinspired and amplified sensitivity piezoresistive sensor provides a promising strategy for the rapid development of next-generation wearable bioelectronics.

Vibrational sum frequency generation (SFG) spectroscopy has been utilized to study the spatial orientation and alignment of Re(CO) 3 Cl(dcbpy) (dcbpy = 4,4′-dicarboxy-2,2′-bipyridine) (or ReC0A) on the (001) and ( 110) surfaces of rutile single-crystalline TiO 2 . The SFG intensity of the CO stretching modes shows an isotropic distribution on the (001) surface and an anisotropic distribution on the (110) surfaces with respect to the in-plane rotation of the crystal relative to the surface normal (or the incident laser beam plane). By combining these results with ab initio SFG simulations and with modeling of ReC0A−TiO 2 cluster binding structures at the density functional theory level, we reveal that the origin of the optical anisotropy for ReC0A on the TiO 2 (110) surface is associated with the binding preference of ReC0A along the [−110] axis. Along this direction, the binding structure is energetically favorable, because of the formation of proper hydrogen bonding between the carboxylate group and passivating water molecules adsorbed on the TiO 2 (110) surface. Simulations of dimers of ReC0A molecules binding close together with full nearest-neighbor effects give a structure that reproduces the experimental SFG polar plot. The tilt angle, defined by the bpy ring angle relative to the surface normal, of the catalyst is found to be 26°for one monomer and 18°for the other, which corresponds to an aggregate at high surface coverage.

Sum frequency generation spectroscopy (SFG) and calculations of SFG spectra based on density functional theory are combined to elucidate the orientation of two Re­(R-2,2′-bipyridine)­(CO)3Cl (R = 4-cyano or 4,4′-dicyano) electrocatalysts when adsorbed on conductive gold surfaces. We find that the electrocatalysts lean on the Au surface to orient the plane of the bipyridine ligand at 63° relative to the surface normal. While the weak binding of the complexes to the gold surface precluded the ability to perform surface immobilized catalysis, homogeneous electrochemical experiments show that the molecular catalysts are active toward the reduction of CO2 to CO and carbonate in the triply reduced state (TOF of 13.3 and 7.2 s–1 for the doubly and singly substituted complexes, respectively). These findings demonstrate the capabilities of the approach of including rigorous spectroscopic and theoretical methods for revealing the conformation and orientation of CO2 reduction catalysts bound to electrode surfaces, which are critical considerations for redox state transitions and catalytic turnover.

HIGHLIGHTS • An overview of the formation mechanisms, fabrication methods, and applications of bioinspired wrinkling patterns on curved substrates is provided. • The effect of substrate curvature is described in detail to clarify the difference of wrinkling patterns between planar and curved substrates. • Opportunities and challenges of the surface wrinkling in the biofabrication, three-dimensional micro/nano fabrication, and fourdimensional printing are discussed.

Gyrification in the human brain is driven by the compressive stress induced by the tangential expansion of the cortical layer, while similar topographies can also be induced by the tangential shrinkage of the spherical substrate. Herein we introduce a simple three-dimensional (3D) shrinking method to generate the cortex-like patterns using two-dimensional (2D) graphene oxide (GO) as the building blocks. By rotation-dip-coating a GO film on an air-charged latex balloon and then releasing the air slowly, a highly folded hydrophobic GO surface can be induced. Wrinkling-to-folding transition was observed and the folding state can be easily regulated by varying the prestrain of the substrate and the thickness of the GO film. Driven by the residue stresses stored in the system, sheet-to-tube actuating occurs rapidly once the bilayer system is cut into slices. In response to some organic solvents, however, the square bilayer actuator exhibits excellent reversible, bidirectional, large-deformational curling properties on wetting and drying. An ultralarge curvature of 2.75 mm was observed within 18 s from the original negative bending to the final positive bending in response to tetrahydrofuran (THF). In addition to a mechanical hand, a swimming worm, a smart package, a bionic mimosa, and two bionic flowers, a crude oil collector has been designed and demonstrated, aided by the superhydrophobic and superoleophilic modified GO surface and the solvent-responsive bilayer system.

Plasmonic metal nanoparticles exhibit large dipole moments upon photoexcitation and have the potential to induce electronic transitions in nearby materials, but fast internal relaxation has to date limited the spatial range and efficiency of plasmonic mediated processes. In this work, we use photo-electrochemistry to synthesize hybrid nanoantennas comprised of plasmonic nanoparticles with photoconductive polymer coatings. We demonstrate that the formation of the conductive polymer is selective to the nanoparticles and that polymerization is enhanced by photoexcitation. In situ spectroscopy and simulations support a mechanism in which up to 50% efficiency of nonradiative energy transfer is achieved. These hybrid nanoantennas combine the unmatched light-harvesting properties of a plasmonic antenna with the similarly unmatched device processability of a polymer shell.