Sponge-shaped Au nanoparticles: a stand-alone metallic photocatalyst for driving the light-induced CO2reduction reaction.

Coinage metal nanoparticles (NPs) enable plasmonic catalysis by generating hot carriers that drive chemical reactions. Making NPs porous enhances the adsorption of reactant molecules. We present a dewetting and dealloying strategy to fabricate porous gold nanoparticles (Au-Sponge) and compare their CO2photoreduction activity with respect to the conventional gold nanoisland (Au-Island) morphology. Porous gold nanoparticles exhibit an unusually broad and red-shifted plasmon resonance which is in agreement with the results of finite difference time domain (FDTD) simulations. The key insight of this work is that the multi-step reduction of CO2driven by short-lived hot carriers generated by the d → s interband transition proceeds extremely quickly as evidenced by the generation of methane. A 3.8-fold enhancement in the photocatalytic performance is observed for the Au-Sponge in comparison to the Au-Island. Electrochemical cyclic voltammetry measurements confirm the 2.5-fold increase in the surface area and roughness factor of the Au-Sponge sample due to its porous nature. Our results indicate that the product yield is limited by the amount of surface adsorbates i.e. reactant-limited. Isotope-labeled mass spectrometry using13CO2was used to confirm that the reaction product (13CH4) originated from CO2photoreduction. We also present the plasmon-mediated photocatalytic transformation of 4-aminothiophenol (PATP) into p,p'-dimercaptoazobenzene (DMAB) using Au-Sponge and Au-Island samples.

Revealing and Attenuating the Electrostatic Properties of Tubulin and Its Polymers.

Tubulin is an electrostatically negative protein that forms cylindrical polymers termed microtubules, which are crucial for a variety of intracellular roles. Exploiting the electrostatic behavior of tubulin and microtubules within functional microfluidic and optoelectronic devices is limited due to the lack of understanding of tubulin behavior as a function of solvent composition. This work displays the tunability of tubulin surface charge using dimethyl sulfoxide (DMSO) for the first time. Increasing the DMSO volume fractions leads to the lowering of tubulin's negative surface charge, eventually causing it to become positive in solutions >80% DMSO. As determined by electrophoretic mobility measurements, this change in surface charge is directionally reversible, i.e., permitting control between -1.5 and + 0.2 cm2  (V s)-1 . When usually negative microtubules are exposed to these conditions, the positively charged tubulin forms tubulin sheets and aggregates, as revealed by an electrophoretic transport assay. Fluorescence-based experiments also indicate that tubulin sheets and aggregates colocalize with negatively charged g-C3 N4 sheets while microtubules do not, further verifying the presence of a positive surface charge. This study illustrates that tubulin and its polymers, in addition to being mechanically robust, are also electrically tunable.

Synthesis, characterization, and visible light photocatalytic activity of solution-processed free-standing 2D Bi2O2Se nanosheets.

Owing to their unique structural and electronic properties such as layered structure with tuneable bandgap and high electron mobility, 2D materials have emerged as promising candidates for photocatalysis. Recently, bismuth oxyselenide (Bi2O2Se), a member of bismuth oxychalcogenide's family has shown great potential in high-speed field-effect transistors, infrared photodetectors, ferroelectric devices, and electrochemical sensors. However, the potential of Bi2O2Se in photocatalysis has not yet been explored. In the current work, Bi2O2Se nanosheets with an average size of ∼170 nm and a lattice strain of 0.01 were synthesized at room temperature using a facile solution-processed method and the as-synthesized material was investigated with various characterization techniques such as x-ray diffraction, FE-SEM, UV-vis spectroscopy. The bandgap for the indirect transition in Bi2O2Se nanosheets was estimated to be 1.19 eV. Further, the visible-light-driven photocatalytic degradation of methylene blue (MB) dye using Bi2O2Se as a photocatalyst is presented. The photocatalytic experiments demonstrate the promising photocatalytic ability of Bi2O2Se as it leads to 25.06% degradation of MB within 80 min of light illumination. The effect of active species trapping agents (carrier and radical scavengers) on photocatalytic activity is also presented and discussed.

Plasmonic photocatalysis and SERS sensing using ellipsometrically modeled Ag nanoisland substrates.

Silver nanoislands are key platforms for plasmonic photocatalysis, SERS sensing and optical metamaterials due to their localized surface plasmon resonances. The low intrinsic loss in Ag enables high local electromagnetic field enhancements. Solution-based fabrication techniques, while cheap, result in highly non-reproducible plasmonic substrates with wide sample-to-sample variability in geometry, optical resonances and Q-factors. Herein, we present a non-lithographic method of forming silver nanoislands based on sputter deposition of Ag films followed by elevated temperature annealing to induce spontaneous dewetting. The resulting plasmonic substrates show reproducible, well-defined LSPR resonances with high ensemble Q-factors whose optical properties could be modeled using spectroscopic ellipsometry to yield n and k values across the visible range. UV-Vis-NIR, and XRD analyses define the optical and crystallographic characteristics of the Ag nanoisland samples. FESEM was utilized to discern the geometry and architecture of the Ag nanoisland as well as their uniformity and monodispersity. Our vacuum deposited Ag nanoislands demonstrated excellent photocatalytic activity for the transformation of 4-nitrobenzenethiol (4-NBT) and 4-aminothiophenol (PATP) into p,p'-dimercaptoazobenzene (DMAB).

Preferentially oriented TiO2 nanotube arrays on non-native substrates and their improved performance as electron transporting layer in halide perovskite solar cells.

Anodically formed TiO2 nanotube arrays (TNTAs) constitute an optoelectronic platform that is being studied for use as a photoanode in photoelectrocatalytic cells, as an electron transport layer (ETL) in solar cells and photodetectors, and as an active layer for chemiresistive and microwave sensors. For optimal transport of charge carriers in these one-dimensional polycrystalline ordered structures, it is desirable to introduce a preferential texture with the grains constituting the nanotube walls aligned along the transport direction. Through x-ray diffraction analysis, we demonstrate that choosing the right water content in the anodization electrolyte and the use of a post-anodization zinc ion treatment can introduce a preferential texture in sub-micron length transparent TNTAs formed on non-native substrates. The incorporation of 1.5 atom% of Zn in TiO2 nanotubes prior to annealing, was found to consistently result in the strongest preferential orientation along the [001] direction. [001] oriented TNTAs exhibited a responsivity of 523 A W-1 at a bias of 2 V for 365 nm photons, which is among the highest reported performance values for ultraviolet photodetection using titania nanotubes. Furthermore, the textured nanotubes without a Zn2+ treatment showed a significantly enhanced performance in halide perovskite solar cells that used TNTAs as the ETL.

Harvesting Hot Holes in Plasmon-Coupled Ultrathin Photoanodes for High-Performance Photoelectrochemical Water Splitting.

The harvesting of hot carriers produced by plasmon decay to generate electricity or drive a chemical reaction enables the reduction of the thermalization losses associated with supra-band gap photons in semiconductor photoelectrochemical (PEC) cells. Through the broadband harvesting of light, hot-carrier PEC devices also produce a sensitizing effect in heterojunctions with wide-band gap metal oxide semiconductors possessing good photostability and catalytic activity but poor absorption of visible wavelength photons. There are several reports of hot electrons in Au injected over the Schottky barrier into crystalline TiO2 and subsequently utilized to drive a chemical reaction but very few reports of hot hole harvesting. In this work, we demonstrate the efficient harvesting of hot holes in Au nanoparticles (Au NPs) covered with a thin layer of amorphous TiO2 (a-TiO2). Under AM1.5G 1 sun illumination, photoanodes consisting of a single layer of ∼50 nm diameter Au NPs coated with a 10 nm shell of a-TiO2 (Au@a-TiO2) generated 2.5 mA cm-2 of photocurrent in 1 M KOH under 0.6 V external bias, rising to 3.7 mA cm-2 in the presence of a hole scavenger (methanol). The quantum yield for hot-carrier-mediated photocurrent generation was estimated to be close to unity for high-energy photons (λ < 420 nm). Au@a-TiO2 photoelectrodes produced a small positive photocurrent of 0.1 mA cm-2 even at a bias of -0.6 V indicating extraction of hot holes even at a strong negative bias. These results together with density functional theory modeling and scanning Kelvin probe force microscope data indicate fast injection of hot holes from Au NPs into a-TiO2 and light harvesting performed near-exclusively by Au NPs. For comparison, Au NPs coated with a 10 nm shell of Al2O3 (Au@Al2O3) generated 0.02 mA cm-2 of photocurrent in 1 M KOH under 0.6 V external bias. These results underscore the critical role played by a-TiO2 in the extraction of holes in Au@a-TiO2 photoanodes, which is not replicated by an ordinary dielectric shell. It is also demonstrated here that an ultrathin photoanode (<100 nm in maximum thickness) can efficiently drive sunlight-driven water splitting.

Asymmetric Multipole Plasmon-Mediated Catalysis Shifts the Product Selectivity of CO2 Photoreduction toward C2+ Products.

Cu/TiO2 is a well-known photocatalyst for the photocatalytic transformation of CO2 into methane. The formation of C2+ products such as ethane and ethanol rather than methane is more interesting due to their higher energy density and economic value, but the formation of C-C bonds is currently a major challenge in CO2 photoreduction. In this context, we report the dominant formation of a C2 product, namely, ethane, from the gas-phase photoreduction of CO2 using TiO2 nanotube arrays (TNTAs) decorated with large-sized (80-200 nm) Ag and Cu nanoparticles without the use of a sacrificial agent or hole scavenger. Isotope-labeled mass spectrometry was used to verify the origin and identity of the reaction products. Under 2 h AM1.5G 1-sun illumination, the total rate of hydrocarbon production (methane + ethane) was highest for AgCu-TNTA with a total CxH2x+2 rate of 23.88 µmol g-1 h-1. Under identical conditions, the CxH2x+2 production rates for Ag-TNTA and Cu-TNTA were 6.54 and 1.39 µmol g-1 h-1, respectively. The ethane selectivity was the highest for AgCu-TNTA with 60.7%, while the ethane selectivity was found to be 15.9 and 10% for the Ag-TNTA and Cu-TNTA, respectively. Adjacent adsorption sites in our photocatalyst develop an asymmetric charge distribution due to quadrupole resonances in large metal nanoparticles and multipole resonances in Ag-Cu heterodimers. Such an asymmetric charge distribution decreases adsorbate-adsorbate repulsion and facilitates C-C coupling of reaction intermediates, which otherwise occurs poorly in TNTAs decorated with small metal nanoparticles.

Nonlithographic Formation of Ta2O5 Nanodimple Arrays Using Electrochemical Anodization and Their Use in Plasmonic Photocatalysis for Enhancement of Local Field and Catalytic Activity.

We demonstrate the formation of Ta2O5 nanodimple arrays on technologically relevant non-native substrates through a simple anodization and annealing process. The anodizing voltage determines the pore diameter (25-60 nm), pore depth (2-9 nm), and rate of anodization (1-2 nm/s of Ta consumed). The formation of Ta dimples after delamination of Ta2O5 nanotubes occurs within a range of voltages from 7 to 40 V. The conversion of dimples from Ta into Ta2O5 changes the morphology of the nanodimples but does not impact dimple ordering. Electron energy loss spectroscopy indicated an electronic band gap of 4.5 eV and a bulk plasmon band with a maximum of 21.5 eV. Gold nanoparticles (Au NPs) were coated on Ta2O5 nanodimple arrays by annealing sputtered Au thin films on Ta nanodimple arrays to simultaneously form Au NPs and convert Ta to Ta2O5. Au NPs produced this way showed a localized surface plasmon resonance maximum at 2.08 eV, red-shifted by ∼0.3 eV from the value in air or on SiO2 substrates. Lumerical simulations suggest a partial embedding of the Au NPs to explain this magnitude of the red shift. The resulting plasmonic heterojunctions exhibited a significantly higher ensemble-averaged local field enhancement than Au NPs on quartz substrates and demonstrated much higher catalytic activity for the plasmon-driven photo-oxidation of p-aminothiophenol to p,p'-dimercaptoazobenzene.

Consistently High Voc Values in p-i-n Type Perovskite Solar Cells Using Ni3+-Doped NiO Nanomesh as the Hole Transporting Layer.

Leading edge p-i-n type halide perovskite solar cells (PSCs) severely underperform n-i-p PSCs. p-i-n type PSCs that use PEDOT:PSS hole transport layers (HTLs) struggle to generate open-circuit photovoltage values higher than 1 V. NiO HTLs have shown greater promise in achieving high Voc values albeit inconsistently. In this report, a NiO nanomesh with Ni3+ defect grown by the hydrothermal method was used to obtain PSCs with Voc values that consistently exceeded 1.10 V (champion Voc = 1.14 V). A champion device photoconversion efficiency of 17.75% was observed. Density functional theory modeling was used to understand the interfacial properties of the NiO/perovskite interface. The PCE of PSCs constructed using the Ni3+-doped NiO nanomesh HTL was ∼34% higher than that of conventional compact NiO-based perovskite solar cells. A suite of characterization techniques such as transmission electron microscopy, field emission scanning electron microscopy, intensity-modulated photocurrent spectroscopy, intensity-modulated photovoltage spectroscopy, time-resolved photoluminescence, steady-state photoluminescence, and Kelvin probe force microscopy provided evidence of better film quality, enhanced charge transfer, and suppressed charge recombination in PSCs based on hydrothermally grown NiO nanostructures.