Photochemical Deposition Research Articles

Photochemical Fabrication of Ag‐Modified Hierarchical Cu@Cu2O/CuO Nanocomposite Toward Room Temperature NO2 Detection

Developing room temperature (RT) gas sensor based on metal oxide semiconductor material has long been challenging. Herein, a 1D hierarchical Ag‐modified Cu@Cu2O/CuO nanocomposite has been designed by low‐temperature etching self‐assembly combined with photochemical deposition method based on Cu nanowires (NWs). After a step of alkaline solution etching, the surface of Cu NWs is self‐assembled to form a hierarchical Cu@Cu2O/CuO, and then Ag nanoparticles are modified on its surface by photochemical deposition to obtain the desired material. All the preparation processes are carried out at RT and have good controllability. When applied as sensing material, the optimal Cu@Cu2O/CuO/Ag nanocomposite exhibits high response of ≈337.0 to 10 ppm NO2 with excellent selectivity and fast response/recovery (60/400 s) at 25 °C. It is worth noting that such a strategy of loading Ag nanoparticles improves its gas sensitivity by about 42.4 times, and the resulting sensor shows good sensitivity and screening ability to NO2 in the low concentration range. Finally, the nanostructure of the material is characterized systematically and the sensing mechanism is discussed.

Plasma-induced surface interactions of Pd/SrTiO3 catalyst for improved performance of photocatalytic degradation of toluene

Defective engineering and the addition of noble metal are effective strategies to realize the high photocatalytic performance of SrTiO3 perovskite. Here, the Pd/SrTiO3 catalyst was successfully prepared by the low-temperature plasma treatment coupling with photochemical deposition of metal Pd, which was applied to the photocatalytic degradation of toluene. Compared with single STO, STON, and Pd-STO catalysts, the prepared Pd-STON catalyst shows the excellent UV photocatalytic performance toward toluene degradation, realizing a ca.80 % degradation efficiency within 90 min reaction time. Based on various characterizations, it revealed that plasma treatment promoted the formation of surface oxygen defects, and strengthened the metal-support interaction. The resultant surface oxygen vacancy accelerated the migration rate of photogenerated electrons and the separation of electrons and holes in space, benefiting for superior performance. It is expected that this study can provide new avenues for the rational design of highly efficient photocatalysts for potential practical applications.

Ag Nanoparticles Deposited onto BaTiO3 Aerogel for Highly Efficient Photodegradation.

Given the increasingly severe environmental problems caused by water pollution, the degradation of organic dyes can be effectively achieved through the utilization of photocatalysis. In this work, metal alkoxides and a combination of alcohol/hydrophobic solvents are employed to prepare BaTiO3 aerogels via a liquid-phase and template-free synthetic route. The preparation process of the aerogels solely entails facile agitation and supercritical drying, eliminating the need for additional heat treatment. The binary solvent of ethanol and toluene is identified as the optimal choice, resulting in a significantly enhanced surface area (up to 223 m2/g) and an abundant pore structure of BaTiO3 aerogels compared to that of the BaTiO3 nanoparticles. Thus, the removal efficiency of the BaTiO3 aerogel sample for MO is nearly twice as high as that of the BaTiO3 nanoparticles sample. Noble metal Ag nanoparticles' deposition onto the BaTiO3 aerogel surface is further achieved via the photochemical deposition method, which enhances the capture of photogenerated electrons, thereby ensuring an elevated level of photocatalytic efficiency. As a result, Ag nanoparticles deposited on BaTiO3 aerogel can degrade MO completely after 40 min of illumination, while the corresponding aerogel before modification can only remove 80% of MO after 60 min. The present work not only complements the preparatory investigation of intricate aerogels but also offers a fresh perspective for the development of diverse perovskite aerogels with broad applications.

Ag-modified enhance the performances of ZnO@CFs based omnidirectional photoelectrochemical ultraviolet detectors

There are several prospective applications for omnidirectional ultraviolet (UV) detectors and underwater detection detectors in optical systems and optical fields. In this work, ZnO nanorods arrays were grown on carbon fibers (CFs). An appropriate amount of Ag nanoparticles (NPs) was deposited on the surface of ZnO nanorods by photochemical deposition. This improved the performance of photoelectrochemical (PEC) based UV detectors. Under 365 nm and 10 mW cm−2 UV irradiation, the photocurrent density of the 30s-Ag/ZnO@CFs based PEC UV detector can reach 1.28 mA cm−2, which is about 7 times that of the ZnO@CFs based PEC UV detector, and the rising time is shortened from 0.17 to 0.10 s. The reason is that increased absorption of ultraviolet light induced by the localized surface plasmon resonance. In addition, the detector exhibits a good flexibility and remains flexible after hundreds of bends and twists. Moreover, the detector is responsive in the range of rotation angle from 0° to 360°. It provides an insight to improve the photoelectric performance and underwater omnidirectional detection ability of the PEC UV detector.

Electronic Structure Engineering of Pt-Ni Alloy NPs by Coupling of Gold Single Atoms on N-Doped Carbon for Highly Efficient Oxygen Reduction Reaction and Hydrogen Evolution Reaction.

Improving the catalytic activity and durability of platinum-based alloy catalysts remains a formidable challenge in the context of renewable energy electrolysis applications. Herein, a facile and rapid photochemical deposition strategy for the synthesis of gold single atoms (Au SAs) anchored on N-doped carbon is presented. These Au SAs serve as a charge redistribution support for Pt-Ni alloy nanoparticles (PtNiNPs/AuSA-NDC), creating an extended electron-donating interface with Pt-Ni alloy sites. Consequently, the PtNiNPs/AuSA-NDC hybrid catalyst manifests exceptional catalytic performance and durability in both the oxygen reduction reaction (ORR) and hydrogen evolution reaction (HER) under acidic conditions. Specifically, in ORR, it exhibits a half-wave potential (0.92V vs RHE), with a mass activity 20.4 times superior to Pt/C at 0.9V. In HER, PtNiNPs/AuSA-NDC demonstrates a notably reduced overpotential of 19.1mV vs RHE at 10mAcm-2 and a mass activity 38 times higher than Pt/C (at 0.25mV). Furthermore, this hybrid catalyst displays outstanding durability, with only an 8.0mV decay observed for ORR and a 6.9mV decay for HER after 10000 cycles. Theoretical calculations provide insight into the mechanism, demonstrating that isolated Au sites effectively modulate the electronic structure of Pt-Ni alloy sites, facilitating intermediate adsorption and enhancing reaction kinetics.

In-situ Ag SPR assisted S-scheme ZnO-CdS multi-layer core-shell heterojunction for enhanced photocatalytic degradation: Energy band engineering and reactive dynamics

Constructing an efficient photocatalyst to accelerate charge separation with strong redox capacity is in pursuit all the way. Herein, a novel heterojunction was achieved for efficient organic degradation, which took advantages of S-scheme mechanism, metal surface plasma resonance (SPR) and unique morphology. The multi-layer core-shell structure can be regulated by aging time with template-free, and Ag nanoparticles were modified on the heterojunction by photochemical deposition in situ to facilitate electron transport and improve stability. S-scheme and SPR endues the heterojunction with broad light absorption, increased light utilization, efficient carrier separation, and strong redox capacity. An examination of reactive dynamics revealed that superoxide radicals and hydroxyl radicals are crucial for oxidative degradation. Introducing oxygen during the reaction process has been found to enhance the efficiency by 7 %. This article furnishes novel insights into a coordination of energy band engineering, structure regulation, as well as reaction process adjustment for facilitating photo-degradation reactions.

WO3 Nanoplates Decorated with Au and SnO2 Nanoparticles for Real-Time Detection of Foodborne Pathogens.

Nowadays, metal oxide semiconductor gas sensors have diverse applications ranging from human health to smart agriculture with the development of Internet of Things (IoT) technologies. However, high operating temperatures and an unsatisfactory detection capability (high sensitivity, fast response/recovery speed, etc.) hinder their integration into the IoT. Herein, a ternary heterostructure was prepared by decorating WO3 nanoplates with Au and SnO2 nanoparticles through a facial photochemical deposition method. This was employed as a sensing material for 3-hydroxy-2-butanone (3H-2B), a biomarker of Listeria monocytogenes. These Au/SnO2-WO3 nanoplate-based sensors exhibited an excellent response (Ra/Rg = 662) to 25 ppm 3H-2B, which was 24 times higher than that of pure WO3 nanoplates at 140 °C. Moreover, the 3H-2B sensor showed an ultrafast response and recovery speed to 25 ppm 3H-2B as well as high selectivity. These excellent sensing performances could be attributed to the rich Au/SnO2-WO3 active interfaces and the excellent transport of carriers in nanoplates. Furthermore, a wireless portable gas sensor equipped with the Au/SnO2-WO3 nanoplates was assembled, which was tested using 3H-2B with known concentrations to study the possibilities of real-time gas monitoring in food quality and safety.

Laser Irradiation Synthesis of AuPd Alloy with Decreased Alloying Degree for Efficient Ethanol Oxidation Reaction.

The preparation of electrocatalysts with high performance for the ethanol oxidation reaction is vital for the large-scale commercialization of direct ethanol fuel cells. Here, we successfully synthesized a high-performance electrocatalyst of a AuPd alloy with a decreased alloying degree via pulsed laser irradiation in liquids. As indicated by the experimental results, the photochemical effect-induced surficial deposition of Pd atoms, combined with the photothermal effect-induced interdiffusion of Au and Pd atoms, resulted in the formation of AuPd alloys with a decreased alloying degree. Structural characterization reveals that L-AuPd exhibits a lower degree of alloying compared to C-AuPd prepared via the conventional co-reduction method. This distinct structure endows L-AuPd with outstanding catalytic activity and stability in EOR, achieving mass and specific activities as high as 16.01 A mgPd-1 and 20.69 mA cm-2, 9.1 and 5.2 times than that of the commercial Pd/C respectively. Furthermore, L-AuPd retains 90.1% of its initial mass activity after 300 cycles. This work offers guidance for laser-assisted fabrication of efficient Pd-based catalysts in EOR.

Construction of Au/ZnWO4/CdS Ternary Photocatalysts with Oxygen Vacancy Modification for Efficient Photocatalytic Hydrogen Production

AbstractRational design and optimization of the photocatalyst architecture, aimed at effectively enhancing light absorption and accelerating charge separation and transfer, can lead to the accomplishment of sustainable photocatalytic hydrogen production. In this study, a ternary system of Au/ZnWO4/CdS is prepared with oxygen vacancy modification through a combination of hydrothermal, chemical precipitation, and photochemical deposition methods. The addition of CdS and Au nanoparticles significantly enhances the light absorption range of ZnWO4 (ZWO) and creates more active sites for hydrogen production. The type‐II engineered heterojunction, in combination with Au as a cocatalyst, is a viable and efficient method for enhancing the separation and transport of electron–hole pairs, thereby facilitating the effective precipitation of hydrogen through photocatalysis. 5A10ZC exhibits a hydrogen production rate of 5483.62 µmol g−1 h−1, which is 167 times higher than that of unmodified ZWO and 29 times higher than that of pure CdS. In addition, it exhibits excellent cycle stability in the hydrogen production cycle stability test. The photoelectrochemical test results show that the construction of the system improves the separation and transfer efficiency of photogenerated carriers. This study provides a new inspiration for the construction of high‐performance photocatalytic materials.

Multiflower-like ReS2/NiAl-LDH Heterojunction for Visible-Light-Driven Photocatalytic CO2 Reduction.

The development of high-efficiency heterojunction photocatalysts has been recognized as an effective approach to facilitate photocatalytic CO2 reduction. In this research, we successfully synthesized a novel multiflower-like ReS2/NiAl-LDH heterojunction through a hydrothermal method. Remarkably, when exposed to visible-light irradiation, 2-ReS2/NiAl-LDH demonstrated an exceptional CO production rate of 272.26 μmol·g-1·h-1, which was 4.0 and 10.8 times higher than that of pristine NiAl-LDH and ReS2. The intertwined structure of ReS2 and NiAl-LDH promoted the efficient transfer and separation of photogenerated carriers, thereby significantly enhancing the photocatalytic CO2 reduction capabilities of the ReS2/NiAl-LDH. Furthermore, the carrier transfer pathway for the 2-ReS2/NiAl-LDH heterojunction was elucidated, suggesting a type II scheme mechanism, as evidenced by photochemical deposition experiments. The findings of this study offer valuable insights and pave the way for future research in the design and construction of LDH-based and ReS2-based heterojunctions for efficient photocatalytic CO2 reduction.

Integration of a recyclable silver substrate for in situ surface-enhanced Raman spectroscopy in digital microfluidics.

We report a new chip-integrated recyclable SERS substrate, achieved by photochemical deposition of silver nanoparticles onto titanium dioxide (TiO2) thin film. Facilitated by the photocatalytic activity of titanium dioxide the SERS substrate can be recycled for multiple analysis. This enables quasi-real time detection of various compounds in an automated and reusable DMF-SERS platform.

Selector-less crossbar array resistive RAM based on TiO2 fabricated by photochemical metal-organic deposition

In this study, we demonstrated a TiO2-based 32 × 32 crossbar array resistive RAM (ReRAM), a promising candidate for next-generation non-volatile memory (NVM), by utilizing a photochemical metal-organic deposition (PMOD) process. We achieved an interface-type resistive switching device with rectifying characteristics by controlling the oxidation state of directly patterned TiOx films through post-heat treatment. The photochemical reaction induced by UV in the PMOD process and the anatase phase formation during the post-heat treatment were analyzed using Fourier-transform infrared spectroscopy, X-ray diffraction, and X-ray photoelectron spectroscopy (XPS). XPS analysis revealed the immediate formation of Ti peroxide post-PMOD process, underscoring the efficacy of post-heat treatments in controlling oxidation states. Employing 350 °C annealed TiOX as the active material, we successfully fabricated a high-yield (93%), selectorless 32 × 32 crossbar array architecture for ReRAM. Our findings highlight the PMOD process as a viable, cost-effective alternative for memory devices, offering optimized oxidation states crucial for the performance of redox-based ReRAM.

Streamlines of the Poynting Vector and Chirality Flux around a Plasmonic Bowtie Nanoantenna.

The streamlines of the energy flux (Poynting vectors) and chirality flux as well as the intensity of the electric field around various plasmonic nanostructures (nanocube, nanocuboid, nanotriangle, hexagonal nanoplate and bowtie nanoantenna) induced by a circularly polarized (CP) or linearly polarized (LP) light were studied theoretically. The boundary element method combined with the method of moment was used to solve a set of surface integral equations, based on the Stratton-Chu formulation, for analyzing the highly distorted electromagnetic (EM) field in the proximity of these nanostructures. We discovered that the winding behavior of these streamlines exhibits versatility for various modes of the surface plasmon resonance of different nanostructures. Recently, using plasmonic nanostructures to facilitate a photochemical reaction has gained significant attention, where the hot carriers (electrons) play important roles. Our findings reveal a connection between the flow pattern of energy flux and the morphology of the photochemical deposition around various plasmonic nanostructures irradiated by a CP light. For example, numerical results exhibit vertically helical streamlines of the Poynting vector around an Au nanocube and transversely twisted-roll streamlines around a nanocuboid. Additionally, the behaviors of the winding energy and chirality fluxes at the gap and corners of a plasmonic bowtie nanoantenna, implying a highly twisted EM field, depend on the polarization of the incident LP light. Our analysis of the streamlines of the Poynting vector and chirality flux offers an insight into the formation of plasmon-enhanced photocatalysis.

Assessing Proton and Hydrogen Permeabilities for Nanoscopic Oxide Coatings Using a Rotating Disk Electrode

The transport of protons and molecular hydrogen (H2) are of relevance to a wide range of electrochemical applications ranging from fuel cells and electrolyzers to sensors and photoelectrochemical cells. One way to modulate the flux of these species to improve device performance such as selectivity and efficiency is to encapsulate electrodes with semi-permeable oxide coatings. [1-3] Thus, knowing the permeabilities of these species within thin oxide layers is of great importance for guiding the design of electrodes and devices. Towards this end, we have employed a modified rotating disk electrode (RDE) set-up to quantify proton and hydrogen permeabilities through sub- 20 nm thick silicon oxide coatings and understand how these transport properties change as a function of the structural and compositional characteristics of the coatings. Oxide coatings were fabricated by both atomic layer deposition (ALD) and photochemical deposition, and their physical and chemical properties characterized by X-Ray Photoelectron spectroscopy and ellipsometry. Based on measurements of the mass transfer limited current density for the hydrogen evolution and hydrogen oxidation reactions, permeabilities were computed. Species permeabilities are furthermore correlated with membrane density and composition, revealing structure-property-performance relationships that can be used to guide the selection of oxide thickness and processing conditions that will optimize performance for an application of interest.

Sn and dual-oxygen-vacancy in the Z-scheme Bi2Sn2O7/Sn/NiAl-layered double hydroxide heterojunction synergistically enhanced photocatalytic activity toward carbon dioxide reduction

Photocatalytic conversion of carbon dioxide (CO2) into high value-added chemicals is an attractive yet challenging process, primarily due to the readily recombination of hole-electron pairs in photocatalysts. Herein, dual-oxygen-vacancy mediated Z-scheme Bi2Sn2O7/Sn/NiAl-layered double hydroxide (VO,O-20BSL) heterojunctions were hydrothermally synthesized and subsequently modified with Sn monomers to enhance photocatalytic activity toward CO2 reduction. The abundance of oxygen vacancies endowed the VO,O-20BSL with extended optical adsorption, enhanced charges separation, and superior CO2 adsorption and activation. The interfacial charges transfer of the VO,O-20BSL was demonstrated to follow a Z-scheme mechanism via photochemical deposition of metal/metal oxide. Under visible light irradiation, the VO,O-20BSL exhibited the highest yields of carbon monoxide (CO) and methane (CH4), with values of 72.03 and 0.85 umol·g−1·h−1, respectively, which were 2.66 and 1.57 times higher than that of the VO-NiAl-layered double hydroxide (VO-1LDH). In situ diffuse reflectance infrared fourier transform spectroscopy (DRIFTS) revealed that carboxylic acid groups (COOH*) and aldehyde groups (CHO*) were the predominant intermediates during CO2 reduction, and accordingly, possible CO2 reduction pathways and mechanism were proposed. This study presents a feasible approach to incorporate dual vacancies into Z-scheme heterojunctions for CO2 reduction.

Ag/Cr-TiO2 and Pd/Cr-TiO2 for Organic Dyes Elimination and Treatment of Polluted River Water in Presence of Visible Light.

In this work, photocatalytic materials constituted by Cr-doped TiO2 (Cr-TiO2) decorated with noble metals show high effectiveness in the mineralization of Acid Orange 7 (AO7) and in the disinfection of real river water. The materials were firstly obtained by sol-gel method to get Cr-TiO2 that was subsequently modified by photochemical deposition of Ag or Pd nanoparticles (Ag/Cr-TiO2, Pd/Cr-TiO2). Chemical-physical characterization results evidenced that the noble metals were homogeneously distributed on the Cr-TiO2 surface. By using Pd(0.25%)/Cr-TiO2, the AO7 discoloration efficiency was about 91.4% after only 60 min of visible irradiation, which can be due to the lowest band gap of this material. Moreover, nitrates, chlorides, total hardness, and coliform bacteria content significantly decreased after the treatment of real river water samples (that is contaminated by industrial and domestic effluents) under UV and visible light irradiation in the presence of TiCrOx decorated with noble metals. One hundred percent of elimination rate for E. coli, total coliforms, and other enterobacteriaceae (without regrowth) was achieved by using Ag/Cr-TiO2 as photocatalyst.

Highly porous ZnO modified with photochemical deposition of silver nanostructure for ultra-sensitive triethylamine detection

Doping noble metals into semiconductor based gas sensors was proved to be an effective strategy in improving gas response properties. Here, we report a silver/silver (II) oxide nanoparticles (Ag/AgO NPs) modified highly porous ZnO nanocomposite. Firstly, the Ag NPs were evenly deposited on the surface of flower-like ZnCO3 precursors through a simple photochemical reduction method, which was then heated at 400 °C to give highly porous Ag/AgO/ZnO nanocomposite, accompaning with the dissociation of ZnCO3 after release of CO2. The interleaving ultrathin and porous sheet-like features of Ag/AgO/ZnO nanocomposite afford it excellent triethylamine (TEA) sensing performance with Ra/Rg = 90.3 at an operating temperature of 240 °C, and the response sensitivity is 5.5-fold higher than that of pure ZnO. Specifically, the porous Ag/AgO/ZnO nanocomposite exhibited a fast response/recovery time of 53 s/8 s and oustanding long-term cyclic stability. The enhanced gas sensing performance can be attributed to the sensitization of Ag/AgO NPs, significantly increasing the number of oxygen vacancies and thus providing more reactive sites. The synergistic interaction between Ag/AgO NPs and porous ZnO nanosheets also facilitates a fast electron transport and a high permeability for gas molecules. This work displays a feasible way of coupling photochemical reduction and pyrolysis strategy to develop highly porous ZnO nanosheets functionalized by noble metal NPs with remarkably enhanced gas response property.

Investigation on the surface charge separation in Pt-supported morphology-related-TiO2 and its effect on water splitting

Lowering Pt loading in the catalyst while maintaining its superior catalytic efficiency during hydrogen evolution reaction (HER) is essential for the large-scale application of water splitting. The utilization of strong metal-support interaction (SMSI) through morphology engineering has emerged as an effective strategy in fabricating Pt-supported catalysts. However, a simple and explicit routine to realize the rational design of morphology-related SMSI remains challenging. Here we report a protocol for the photochemical deposition of Pt, which benefits from the intrinsic difference in absorption capability of TiO2 to establish proper Pt+ species and charge separation domains on the surface. With a comprehensive investigation of the surface environment through experiments and Density functional theory (DFT) calculations, charge transfer from Pt to Ti, the separation of electron-hole pairs, and the enhanced electron transfer in the TiO2 matrix were confirmed. It is reported that H2O molecules can be spontaneously dissociated by the surface Ti and O, generating OH stabilized by adjacent Ti and Pt. Such adsorbed OH group induces changes in the electron density of Pt, consequently favours the H adsorption and enhances the HER. Benefiting from the preferable electronic state, the annealed Pt@TiO2-pH9 (PTO-pH9@A) exhibits an overpotential of 30 mV to reach 10 mA cm−2 geo and a mass activity of 3954 A g-1Pt, which is 17-fold higher than the commercial Pt/C. Our work provides a new strategy for the high-efficient catalyst design by the surface state- regulated SMSI.

Stratospheric Gas‐Phase Production Alone Cannot Explain Observations of Atmospheric Perchlorate on Earth

AbstractPerchlorate has been observed in many environments on Earth and Mars but its sources remain poorly quantified. In this study, we use a global three‐dimensional chemical transport model to simulate perchlorate's gas‐phase photochemical production, atmospheric transport, and deposition on Earth's surface. Model predictions are compared to newly compiled observations of atmospheric concentrations, deposition flux, and oxygen isotopic composition of perchlorate. We find that the modeled gas‐phase production of perchlorate is consistent with reported stratospheric observations. Nevertheless, we show that this mechanism alone cannot explain the high levels of perchlorate observed at many near‐surface sites (aerosol concentrations >0.1 ng m−3 and deposition fluxes >10 g km−2 yr−1) or the low 17O‐excess observed in perchlorate sampled from pristine environments (<+18.4‰). We discuss four hypotheses to explain the model‐observation discrepancies and recommend laboratory and field observations to address key uncertainties in atmospheric sources of perchlorate.

Nanoscopic Silicon Oxide Overlayers Improve the Performance of Ruthenium Oxide Electrocatalysts Toward the Oxygen Evolution Reaction

RuO2 is a highly active electrocatalyst for the oxygen evolution reaction (OER) but is unstable in acidic environments. Herein we investigate the encapsulation of RuO2 nanoparticles with semipermeable, nanoscopic silicon oxide (SiOx) overlayers as a strategy to improve their stability. SiOx encapsulated RuO2 (SiOx|RuO2) electrodes were prepared by drop-casting RuO2 nanoparticles onto glassy carbon substrates followed by deposition of SiOx overlayers of varying thickness by a room temperature photochemical deposition process. The best-performing SiOx|RuO2 electrodes consisted of 2–3 nm thick SiOx overlayers on top of RuO2 particles and 3–7 nm thick SiOx on the glassy carbon substrate. Such electrodes exhibited lower overpotentials relative to bare RuO2 due to an improved electrochemically active surface area while also demonstrating an ability to retain OER activity over time, especially at higher overpotentials. Surprisingly, it was found that the SiOx coating was unable to prevent Ru dissolution, which was found to be proportional to the charge passed and independent of the presence or thickness of the SiOx coating. Thus, other possible explanations for the improved current retention of SiOx|RuO2 electrodes are discussed, including the influences of the overlayer on bubble dynamics and the stability of the underlying glassy carbon substrate.