Photocatalytic Mechanism Control and Study of Carrier Dynamics in CdS@C3N5 Core-Shell Nanowires.

We present a potential solution to the problem of extraction of photogenerated holes from CdS nanocrystals and nanowires. The nanosheet form of C3N5 is a low-band-gap (Eg = 2.03 eV), azo-linked graphenic carbon nitride framework formed by the polymerization of melem hydrazine (MHP). C3N5 nanosheets were either wrapped around CdS nanorods (NRs) following the synthesis of pristine chalcogenide or intercalated among them by an in situ synthesis protocol to form two kinds of heterostructures, CdS-MHP and CdS-MHPINS, respectively. CdS-MHP improved the photocatalytic degradation rate of 4-nitrophenol by nearly an order of magnitude in comparison to bare CdS NRs. CdS-MHP also enhanced the sunlight-driven photocatalytic activity of bare CdS NWs for the decolorization of rhodamine B (RhB) by a remarkable 300% through the improved extraction and utilization of photogenerated holes due to surface passivation. More interestingly, CdS-MHP provided reaction pathway control over RhB degradation. In the absence of scavengers, CdS-MHP degraded RhB through the N-deethylation pathway. When either hole scavenger or electron scavenger was added to the RhB solution, the photocatalytic activity of CdS-MHP remained mostly unchanged, while the degradation mechanism shifted to the chromophore cleavage (cycloreversion) pathway. We investigated the optoelectronic properties of CdS-C3N5 heterojunctions using density functional theory (DFT) simulations, finite difference time domain (FDTD) simulations, time-resolved terahertz spectroscopy (TRTS), and photoconductivity measurements. TRTS indicated high carrier mobilities >450 cm2 V-1 s-1 and carrier relaxation times >60 ps for CdS-MHP, while CdS-MHPINS exhibited much lower mobilities <150 cm2 V-1 s-1 and short carrier relaxation times <20 ps. Hysteresis in the photoconductive J-V characteristics of CdS NWs disappeared in CdS-MHP, confirming surface passivation. Dispersion-corrected DFT simulations indicated a delocalized HOMO and a LUMO localized on C3N5 in CdS-MHP. C3N5, with its extended π-conjugation and low band gap, can function as a shuttle to extract carriers and excitons in nanostructured heterojunctions, and enhance performance in optoelectronic devices. Our results demonstrate how carrier dynamics in core-shell heterostructures can be manipulated to achieve control over the reaction mechanism in photocatalysis.

Hot Electrons in TiO2-Noble Metal Nano-Heterojunctions: Fundamental Science and Applications in Photocatalysis.

Plasmonic photocatalysis enables innovation by harnessing photonic energy across a broad swathe of the solar spectrum to drive chemical reactions. This review provides a comprehensive summary of the latest developments and issues for advanced research in plasmonic hot electron driven photocatalytic technologies focusing on TiO2-noble metal nanoparticle heterojunctions. In-depth discussions on fundamental hot electron phenomena in plasmonic photocatalysis is the focal point of this review. We summarize hot electron dynamics, elaborate on techniques to probe and measure said phenomena, and provide perspective on potential applications-photocatalytic degradation of organic pollutants, CO2 photoreduction, and photoelectrochemical water splitting-that benefit from this technology. A contentious and hitherto unexplained phenomenon is the wavelength dependence of plasmonic photocatalysis. Many published reports on noble metal-metal oxide nanostructures show action spectra where quantum yields closely follow the absorption corresponding to higher energy interband transitions, while an equal number also show quantum efficiencies that follow the optical response corresponding to the localized surface plasmon resonance (LSPR). We have provided a working hypothesis for the first time to reconcile these contradictory results and explain why photocatalytic action in certain plasmonic systems is mediated by interband transitions and in others by hot electrons produced by the decay of particle plasmons.

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.

Effect of morphology on the photoelectrochemical performance of nanostructured Cu2O photocathodes.

Cu2O is a promising earth-abundant semiconductor photocathode for sunlight-driven water splitting. Characterization results are presented to show how the photocurrent density (Jph), onset potential (Eonset), band edges, carrier density (NA), and interfacial charge transfer resistance (Rct) are affected by the morphology and method used to deposit Cu2O on a copper foil. Mesoscopic and planar morphologies exhibit large differences in the values ofNAandRct. However, these differences are not observed to translate to other photocatalytic properties of Cu2O. Mesoscopic and planar morphologies exhibit similar bandgap (e.g.) and flat band potential (Efb) values of 1.93 ± 0.04 eV and 0.48 ± 0.06 eV respectively.Eonsetof 0.48 ± 0.04 eV obtained for these systems is close to theEfbindicating negligible water reduction overpotential. Electrochemically deposited planar Cu2O provides the highest photocurrent density of 5.0 mA cm-2at 0 V vs reversible hydrogen electrode (RHE) of all the morphologies studied. The photocurrent densities observed in this study are among the highest reported values for bare Cu2O photocathodes.

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).

Transition-Path Probability as a Test of Reaction-Coordinate Quality Reveals DNA Hairpin Folding Is a One-Dimensional Diffusive Process.

Chemical reactions are typically described in terms of progress along a reaction coordinate. However, the quality of reaction coordinates for describing reaction dynamics is seldom tested experimentally. We applied a framework for gauging reaction-coordinate quality based on transition-path analysis to experimental data for the first time, looking at folding trajectories of single DNA hairpin molecules measured under tension applied by optical tweezers. The conditional probability for being on a reactive transition path was compared with the probability expected for ideal diffusion over a 1D energy landscape based on the committor function. Analyzing measurements and simulations of hairpin folding where end-to-end extension is the reaction coordinate, after accounting for instrumental effects on the analysis, we found good agreement between transition-path and committor analyses for model two-state hairpins, demonstrating that folding is well-described by 1D diffusion. This work establishes transition-path analysis as a powerful new tool for testing experimental reaction-coordinate quality.

Reconstructing folding energy landscapes from splitting probability analysis of single-molecule trajectories.

Structural self-assembly in biopolymers, such as proteins and nucleic acids, involves a diffusive search for the minimum-energy state in a conformational free-energy landscape. The likelihood of folding proceeding to completion, as a function of the reaction coordinate used to monitor the transition, can be described by the splitting probability, p(fold)(x). P(fold) encodes information about the underlying energy landscape, and it is often used to judge the quality of the reaction coordinate. Here, we show how p(fold) can be used to reconstruct energy landscapes from single-molecule folding trajectories, using force spectroscopy measurements of single DNA hairpins. Calculating p(fold)(x) directly from trajectories of the molecular extension measured for hairpins fluctuating in equilibrium between folded and unfolded states, we inverted the result expected from diffusion over a 1D energy landscape to obtain the implied landscape profile. The results agreed well with the landscapes reconstructed by established methods, but, remarkably, without the need to deconvolve instrumental effects on the landscape, such as tether compliance. The same approach was also applied to hairpins with multistate folding pathways. The relative insensitivity of the method to the instrumental compliance was confirmed by simulations of folding measured with different tether stiffnesses. This work confirms that the molecular extension is a good reaction coordinate for these measurements, and validates a powerful yet simple method for reconstructing landscapes from single-molecule trajectories.