Plasmon-driven Photocatalysis Research Articles

(Invited) Plasmon-Driven Photochemistry for the Synthesis of Metal Nanostructures

Plasmon-driven photocatalysis with metal nanoparticles holds great promise for initiating and controlling chemical reactions at the nanoscale. One interesting application of plasmonic photochemistry involves the synthesis of metal nanostructures from cationic precursors. Despite more than twenty years of study however, this unique approach to material synthesis remains restricted to just two elements: silver (Ag) and gold (Au). To date, this process is yet to be observed with any other metals. Here, we report the plasmon-driven synthesis of copper (Cu) nanoparticles in aqueous solution via a seed-mediated growth strategy. The plasmonic synthesis is amenable to various Cu precursors, but is highly sensitive to the type of hole scavenger used in the reaction. We also found that the exclusion of oxygen from the system, both in the initial synthesis of Cu seeds and in their subsequent growth into larger nanoparticles, was essential for enabling the plasmon-driven process to proceed. A series of control experiments, supported by photoelectrochemical measurements, were performed to confirm that the growth of Cu nanoparticles occurs via plasmon excitation of the Cu seeds. Overall, our approach offers a unique route to the synthesis of Cu nanoparticles and expands the domain of plasmon-driven photochemistry to a new element.

(Invited) Metal and Nonmetal Plasmonic Nanostructures for Surface-Enhanced Raman Spectroscopy Detection

Toxic small molecules such as pesticides, food additives, plasticizers and dyes have been posing increasing threat to human health. Surface-enhanced Raman scattering spectroscopy (SERS) is a powerful sensing strategy for these small molecules with advantages including fast response, high sensitivity and fingerprint identification.Based on the surface plasmon effect, gold and silver nanostructures are the typical plasmonic sensing materials for rapid detection with SERS. However, the crucial challenges for realizing on-site real detection application is to fabricate reproducible and highly sensitive SERS substrates and portable instrument. We fabricated several long-range ordered sensitive nanostructure arrays based on anodic aluminum oxide templates which could provide reproducible structural patterns. Then, we developed a portable instrument integrated with database of the standard Raman spectra of common contaminants and a software for automatic identification and comparison of the test spectrum with the standard database, which can identify the specific analytes. Combined with the sensitive and reproducible SERS substrates, we realized the on-site and rapid detection of various toxic contaminants.Recently, as an inexpensive candidate, nonmetal plasmonic materials like oxide semiconductors have attracted increasing interests, which induced by the increase of free charge carriers via introducing oxygen vacancies. We synthesized oxygen-deficient WO3-x and NayWO3-x nanosheets and realized the localized surface plasmon resonance (LSPR) band in visible range (~530 nm) as same as the gold nanoparticles, which is the bluest. Then, SERS detection of dyes has also been realized on nonmetal substrate. Moreover, the plasmonic oxygen-deficient oxides showed wide LSPR tuning window from visible to infrared range and plasmon-driven photocatalysis, which may open potentials for biological applications.

Quantifying the ultrafast and steady-state molecular reduction potential of a plasmonic photocatalyst.

Plasmonic materials are promising photocatalysts as they are well suited to convert light into hot carriers and heat. Hot electron transfer is suggested as the driving force in many plasmon-driven reactions. However, to date, there are no direct molecular measures of the rate and yield of plasmon-to-molecule electron transfer or energy of these electrons on the timescale of plasmon decay. Here, we use ultrafast and spectroelectrochemical surface-enhanced Raman spectroscopy to quantify electron transfer from a plasmonic substrate to adsorbed methyl viologen molecules. We observe a reduction yield of 2.4 to 3.5% on the picosecond timescale, with plasmon-induced potentials ranging from [Formula: see text]3.1 to [Formula: see text]4.5 mV. Excitingly, some of these reduced species are stabilized and persist for tens of minutes. This work provides concrete metrics toward optimizing material-molecule interactions for efficient plasmon-driven photocatalysis.

Origin of Superlinear Power Dependence of Reaction Rates in Plasmon-Driven Photocatalysis: A Case Study of Reductive Nitrothiophenol Coupling Reactions

The superlinear dependence of the reaction rate on the power of the excitation light, which may arise from both thermal and nonthermal effects, has been a hallmark of plasmon-driven photocatalysis on nanostructured metal surfaces. However, it remains challenging to distinguish and quantify the thermal and nonthermal effects because even slight uncertainties in measuring the local temperatures at the active surface sites may lead to significant errors in assessing thermal and nonthermal contributions to the overall reaction rates. Here we employ surface-enhanced Raman scattering as a surface-sensitive in situ spectroscopic tool to correlate detailed kinetic features of plasmon-mediated molecular transformations to the local temperatures at the active sites on photocatalyst surfaces. Our spectroscopic results clearly reveal that the superlinearity in the power dependence of the reaction rate observed in a plasmon-driven model reaction, specifically the reductive coupling of para-nitrothiophenol adsorbates on Ag nanoparticle surfaces, originates essentially from photothermal heating rather than nonthermal plasmonic effects.

Construction of a novel hybrid plasmonic metal-2D MXene catalyst for plasmon-driven photoreduction of nitroaromatics

Plasmon-driven photocatalysis offers a green and promising strategy for solar-to-chemical energy conversion under mild reaction conditions. Herein, we developed an efficient strategy to significantly enhance the electromagnetic (EM) field in trimetallic Au@Ag@Pd NPs via engineering nanocavity as plasmonic hotspot. More importantly, a novel hybrid system of plasmonic metal-two-dimensional (2D) materials was constructed via loading of Au@Ag@Pd NPs with nanocavities onto the surface of 2D MXene (Ti3C2). The obtained Au@Ag@Pd/Ti3C2 photocatalyst showed superior catalytic performance on plasmon-driven hydrogenation of nitroaromatics even at 0 °C under visible light. Furthermore, it exhibited excellent stability and reusability in photocatalytic process. The EM field was dramatically enhanced via plasmonic component coupling and nanocavities engineered as plasmonic hotspot in the Au@Ag@Pd NPs, which can boost the generation of hot electrons. The presence of Pd and Ti3C2 facilitated the transfer of hot electrons from Au@Ag to Pd and then to MXene, which would prolong lifetimes of hot electrons and improve the utilization of hot electrons. Our present work paves a way to design more efficient hybrid plasmonic catalysts.

Shining at the Tips: Anisotropic Deposition of Pt Nanoparticles Boosting Hot Carrier Utilization for Plasmon-Driven Photocatalysis.

Bimetallic nanostructures are a promising candidate for plasmon-driven photocatalysis. However, knowledge on the generation and utilization of hot carriers in bimetallic nanostructures is still limited. In this work, we explored Pt position-dependent photocatalytic properties of bimetallic Au nanobipyramids (Au NBPs) with single-molecule fluorescence imaging. Compared with all-deposited core-shell nanostructures (aPt-Au NBPs), single-molecule imaging and simulation results show that the end-deposited bimetallic nanostructures (ePt-Au NBPs) can maintain a strong electromagnetic (EM) field and further promote the generation and transfer of energetic hot electrons for photocatalysis. Even though the Pt lattice is more stable than Au, the strong EM field at the sharp tips can boost lattice vibration, where enhanced spontaneous surface restructuring for active reaction site generation takes place. Significantly enhanced catalytic efficiency from ePt-Au NBPs is observed in contrast to that of Au NBPs and aPt-Au NBPs. These microscopic evidences offer valuable guidelines to design plasmon-based photocatalysts, particularly for bimetallic nanostructures.

Synergy of Adsorption and Plasmonic Photocatalysis in the Au-CeO2 Nanosystem: Experimental Validation and Plasmonic Modeling.

Adsorption-mediated water treatment leaves adsorbents as secondary pollutants in the environment. However, photocatalysis aids in decomposing the contaminant into its nontoxic forms. In this context, we demonstrate an adsorption-photocatalysis pairing in Au-CeO2 nanocomposites for a total methylene blue (MB) removal from water. We synthesized Au-CeO2 through the citrate (cit) reduction method at different Au loading and studied its adsorption capacity with kinetics and thermodynamic models. We observe that the high adsorption capacity of Au-CeO2 is primarily because of the presence of Ce3+ states in CeO2 and citrate ligands on Au NPs. The Ce3+ states interact and transfer their electrons to supported Au NPs, rendering a negative charge over Au. The negatively charged Au surface and the carboxyl (-COO-) group of citrate ligands mediate an electrostatic interaction/adsorption of cationic MB. The total removal of MB is expedited under white light and lasers. A control experiment with Au NPs shows less adsorption-photocatalysis. The size of Au NPs and Au-CeO2 interfacial interaction is responsible for the surface plasmon resonance spectral position at 550-600 nm. Linear sweep voltammetry (LSV) and plasmonic field simulation show surface plasmon-driven photocatalysis in Au-CeO2. LSV shows a 3-fold higher photocurrent density in Au-CeO2 than colloidal Au NPs under white light. The simulated electric field intensity in Au-CeO2 is maximum at SPR excitation and the closest interfacial separation (d = 0 nm). The plasmon-driven photocatalysis in colloidal Au NPs is mainly due to the interaction of hot electrons with the adsorbed MB molecule. Notably, near-field light concentration, hot electrons, and interfacial charge separation are responsible for excellent MB removal in the Au-CeO2 nanosystem. The total MB removal through adsorption-photocatalysis pairing is 99.3% (Au-CeO2), 30.7% (Au NPs), and 13% (CeO2).

Plasmon-driven oxidative coupling of aniline-derivative adsorbates: A comparative study of para-ethynylaniline and para-mercaptoaniline.

Plasmon-driven photocatalysis has emerged as a paradigm-shifting approach, based on which the energy of photons can be judiciously harnessed to trigger interfacial molecular transformations on metallic nanostructure surfaces in a regioselective manner with nanoscale precision. Over the past decade, the formation of aromatic azo compounds through plasmon-driven oxidative coupling of thiolated aniline-derivative adsorbates has become a testbed for developing detailed mechanistic understanding of plasmon-mediated photochemistry. Such photocatalytic bimolecular coupling reactions may occur not only between thiolated aniline-derivative adsorbates but also between their nonthiolated analogs. How the nonthiolated adsorbates behave differently from their thiolated counterparts during the plasmon-driven coupling reactions, however, remains largely unexplored. Here, we systematically compare an alkynylated aniline-derivative, para-ethynylaniline, to its thiolated counterpart, para-mercaptoaniline, in terms of their adsorption conformations, structural flexibility, photochemical reactivity, and transforming kinetics on Ag nanophotocatalyst surfaces. We employ surface-enhanced Raman scattering as an in situ spectroscopic tool to track the detailed structural evolution of the transforming molecular adsorbates in real time during the plasmon-driven coupling reactions. Rigorous analysis of the spectroscopic results, further aided by density functional theory calculations, lays an insightful knowledge foundation that enables us to elucidate how the alteration of the chemical nature of metal-adsorbate interactions profoundly influences the transforming behaviors of the molecular adsorbates during plasmon-driven photocatalytic reactions.

In-Situ Monitoring the SERS Spectra of para-Aminothiophenol Adsorbed on Plasmon-Tunable Au@Ag Core-Shell Nanostars.

Plasmon-induced photocatalysis on noble metal surfaces has attracted broad attention due to its application in sunlight energy conversion, while the selectivity of plasmonic platforms remains unclear. Herein, we present the controlled plasmon-mediated oxidation of para-aminothiophenol (p-ATP) by employing Au@Ag core–shell nanostars with tunable tip plasmons in visible–near-infrared range as reactors. In-situ Raman measurements indicate that Au@Ag core–shell nanostars essentially promote the conversion of p-ATP to 4,4′-dimercaptoazobenzene (DMAB) due to hot carriers excited by localized surface plasmon resonance. Au@Ag nanostars with plasmon modes under resonant light excitation suggested higher catalytic efficiency, as evidenced by the larger intensity ratios between 1440 cm−1 (N=N stretching of DMAB) and 1080 cm−1 shifts (C–S stretching of p-ATP). Importantly, the time-dependent surface-enhanced Raman scattering spectra showed that the conversion efficiency of p-ATP was mainly dictated by the resonance condition between the tip plasmon mode of Au@Ag core–shell nanostars and the excitation light, as well as the choice of excitation wavelength. These results show that plasmon bands of metal nanostructures play an important role in the efficiency of plasmon-driven photocatalysis.

MoS2/graphene van der Waals heterojunctions combined with two-layered Au NP for SERS and catalysis analyse.

MoS2-plasmonic hybrid platforms have attracted significant interest in surface-enhanced Raman scattering (SERS) and plasmon-driven photocatalysis. However, direct contact between the metal and MoS2 creates strain that deteriorates the electron transport across the metal/ MoS2 interfaces, which would affect the SERS effect and the catalytic performance. Here, the MoS2/graphene van der Waals heterojunctions (vdWHs) were fabricated and combined with two-layered gold nanoparticles (Au NP) for SERS and plasmon-driven photocatalysis analyse. The graphene film is introduced to provide an effective buffer layer between Au NP and MoS2, which not only eliminates the inhomogeneous contact on MoS2 but also benefits the electron transfer. The substrate exhibits excellent SERS capability realizing ultra-sensitive detection for 4-pyridinethiol molecules. Also, the surface catalytic reaction of p-nitrothiophenol (PNTP) to p,p-dimercaptobenzene (DMAB) conversion was in situ monitored, demonstrating that the vdWHs-plasmonic hybrid could effectively accelerate reaction process. The mechanism of the SERS and catalytic behaviors are investigated via experiments combined with theoretical simulations (finite element method and quantum chemical calculations).

Plasma-Driven Photocatalysis Based on Gold Nanoporous Arrays.

Various effects caused by surface plasmons including enhanced electromagnetic field, local heating, and excited electrons/holes can not only redistribute the electromagnetic field in the time domain and space but also redistribute the excited carriers and drive chemical reactions. In this study, firstly, an Au nanoporous array photocatalyst with the arrayed gauge was prepared by means of the anodic alumina template. Then, the formation of 4,4′-dimercaptoazobenzene (DMAB) by the surface plasmon-driven photocatalysis under 633 nm laser irradiation was investigated by means of Raman spectroscopy using aminothiophenol (PATP) as a probe molecule on gold nananoporous arrays. In addition, sodium borohydride was introduced in situ to realize the reverse photocatalytic reaction driven by the surface plasma. With the help of FDTD software, the plasma distribution characteristics on the surface of Au nanoporous arrays were simulated and analyzed. Through this practical method, it is expected to draw specific graphics, letters, and Chinese characters on the micro/nano scale, and realize the functions of graphics drawing, information encryption, reading, and erasing on the micro/nano scale.

Kinetics and Mechanism of Plasmon-Driven Dehalogenation Reaction of Brominated Purine Nucleobases on Ag and Au.

Plasmon-driven photocatalysis is an emerging and promising application of noble metal nanoparticles (NPs). An understanding of the fundamental aspects of plasmon interaction with molecules and factors controlling their reaction rate in a heterogeneous system is of high importance. Therefore, the dehalogenation kinetics of 8-bromoguanine (BrGua) and 8-bromoadenine (BrAde) on aggregated surfaces of silver (Ag) and gold (Au) NPs have been studied to understand the reaction kinetics and the underlying reaction mechanism prevalent in heterogeneous reaction systems induced by plasmons monitored by surface enhanced Raman scattering (SERS). We conclude that the time-average constant concentration of hot electrons and the time scale of dissociation of transient negative ions (TNI) are crucial in defining the reaction rate law based on a proposed kinetic model. An overall higher reaction rate of dehalogenation is observed on Ag compared with Au, which is explained by the favorable hot-hole scavenging by the reaction product and the byproduct. We therefore arrive at the conclusion that insufficient hole deactivation could retard the reaction rate significantly, marking itself as rate-determining step for the overall reaction. The wavelength dependency of the reaction rate normalized to absorbed optical power indicates the nonthermal nature of the plasmon-driven reaction. The study therefore lays a general approach toward understanding the kinetics and reaction mechanism of a plasmon-driven reaction in a heterogeneous system, and furthermore, it leads to a better understanding of the reactivity of brominated purine derivatives on Ag and Au, which could in the future be exploited, for example, in plasmon-assisted cancer therapy.

Photoelectrochemical Methanol Oxidation Under Visible and UV Excitation of TiO2-Supported TiN and ZrN Plasmonic Nanoparticles

TiN and ZrN refractory transition metal nitride nanoparticles (NPs) have recently emerged as an alternative to noble metals in plasmonic applications. However, plasmon-driven photocatalysis by ZrN NPs is largely unexplored. In this study, optical properties, morphology, crystal structure and surface composition of in-house synthesized and commercial ZrN nanoparticles (NPs) are vigorously characterized in order to select the best candidate material for evaluation of activity towards CH3OH photoelectrochemical oxidation. The photocatalytic activity of TiO2-supported ZrN NPs is compared to that of TiN/TiO2 as a function of NP loading and illumination wavelength. Our results indicate that optical properties and photocatalytic activity of ZrN/TiO2 are strongly affected by ZrN surface oxidation and agglomeration. We found that under visible illumination, both in-house synthesized 17 nm ZrN and commercial 30 nm TiN NPs promote TiO2 activity for CH3OH oxidation, while under visible + UV excitation, an inhibition effect is observed. The differences between the TiN/TiO2 and ZrN/TiO2 interfaces are discussed and the mechanisms of promotion/inhibition of TiO2 photocatalytic activity by ZrN and TiN NPs are proposed. Electromagnetic simulations are used to facilitate interpretation of experimental extinctions and photocatalytic activities.

Photothermal Effect, Local Field Dependence, and Charge Carrier Relaying Species in Plasmon-Driven Photocatalysis: A Case Study of Aerobic Nitrothiophenol Coupling Reaction

Optical excitation of plasmonic electron oscillations confined by metallic nanoparticles provides a unique means of driving unconventional photocatalytic transformations of molecular adsorbates on ...

Controlling Photocatalytic Reactions and Hot Electron Transfer by Rationally Designing Pore Sizes and Encapsulated Plasmonic Nanoparticle Numbers

Controlled self-assembly of different numbers of gold nanoparticles (AuNPs) in the highly ordered cylindrical anodic aluminum oxide nanopores was achieved by a facile ultrasonication method. The surface plasmon resonance bands became red-shifted by increasing the number of nanoparticles (N), in the top view, from monomer M1 (N = 1) to multimers of M2 (N = 3 ± 1), M3 (N = 5 ± 1), and M4 (N = 7 ± 1). The numerical calculations of the M2 model showed the best match of 2 nm nanogap among 28 nm diameter AuNPs in 53 nm diameter nanopores. When the number of AuNPs inside the nanopores increased, more hotspots were generated, which induced the plasmon-driven photocatalysis on AuNP clusters at the incident visible light of 633 nm. The enhanced photocatalytic reaction of 4-nitrobenzenethiol was observed after sequentially increasing the number of AuNPs, which began at M3 and was maximum for M4. The M3 configuration could be a magical number of AuNP clusters for the nanogap-induced photocatalysis under 633 nm irradiation (∼0.2 mW) for 12 min. Our methods should be helpful in adjusting photocatalysis by varying the numbers of nanoparticles inside the tunable nanopores.

Effect of Silica Supports on Plasmonic Heating of Molecular Adsorbates as Measured by Ultrafast Surface-Enhanced Raman Thermometry.

Plasmonic materials show great potential for selective photocatalysis under relatively mild reaction conditions. However, the catalytic activity of these plasmonic catalysts can also depend upon the support material that stabilizes the catalysts, where the composition of the catalytic support may change the overall photocatalytic efficiency and yield. It is unknown how changes in the support material may change the plasmon-driven photocatalysis, which may be initiated by plasmon-derived hot carriers, localized heating, or enhanced electromagnetic fields. Herein, we probe the effects of catalytic supports on heating in plasmon-driven catalysis by examining various gold nanoparticle oxide systems. We use ultrafast surface-enhanced Raman thermometry to measure the effective temperature, equivalent to the vibrational kinetic energy, of reporter molecules located between plasmonic gold nanostructures and local environments ranging from ligands to mesoporous silica shells to silica shells. Upon photoexcitation, the transient effective temperature, equivalent to the energy deposited into a vibrational mode, of adsorbed molecules on the silica-coated samples increases, and the energy quickly dissipates within 3 ps. However, the baseline effective temperature that arises from the surface-enhanced Raman spectroscopy probing process depends upon the encapsulant, where the energy deposition differs by 200-300 K between the ligand-coated (citrate or CTAB) and the silica-coated samples. Adsorbates surrounded by a silica shell experience significantly higher effective temperatures than the adsorbates surrounded by ligands or solvent, likely because of the differing effective heat capacities of these media. Taken together, this work shows that a silica support impacts the localized heating of molecular adsorbates on the gold surface and may play a role in enhanced plasmonic photocatalysis because of increased thermal contributions.

Plasmon-Driven Photocatalysis Leads to Products Known from E-beam and X-ray-Induced Surface Chemistry.

Plasmonic metal nanostructures can concentrate incident optical fields in nanometer-sized volumes, called hot spots. This leads to enhanced optical responses of molecules in such a hot spot but also to chemical transformations, driven by plasmon-induced hot carriers. Here, we employ tip-enhanced Raman spectroscopy (TERS) to study the mechanism of these reactions in situ at the level of a single hot spot. Direct spectroscopic measurements reveal the energy distribution of hot electrons, as well as the temperature changes due to plasmonic heating. Therefore, charge-driven reactions can be distinguished from thermal reaction pathways. The products of the hot-carrier-driven reactions are strikingly similar to the ones known from X-ray or e-beam-induced surface chemistry despite the >100-fold energy difference between visible and X-ray photons. Understanding the analogies between those two scenarios implies new strategies for rational design of plasmonic photocatalytic reactions and for the elimination of photoinduced damage in plasmon-enhanced spectroscopy.

Ultrafast Nanoscale Raman Thermometry Proves Heating Is Not a Primary Mechanism for Plasmon-Driven Photocatalysis.

Plasmonic materials efficiently convert light to various forms of energies for many applications, including photocatalysis, photovoltaics, and photothermal therapies. In particular, plasmonic photocatalysts hold incredible promise for highly selective sunlight-driven catalysis through the generation of highly energetic holes and electrons used to drive chemical reactions. However, plasmons are also known to generate heat, and the partitioning of photoexcitation energy into hot carriers and heat on molecularly relevant time scales is not well understood, yet plays a crucial role in designing and understanding these photocatalysts. Using an ultrafast surface-enhanced Raman thermometry technique, we probe the effective temperature, equivalent to the mode-specific increase of vibrational kinetic energy, of molecules adsorbed to gold nanoparticle aggregates in the most active hot spots on the picosecond time scale of chemical reactivity. This represents the first measurement of vibrational energy deposition for coupled molecular-plasmonic systems on the picosecond time scale of molecular motion. We find that upon plasmon excitation, the adsorbates in the hot spots undergo an initial energy transfer within several picoseconds that changes the effective temperature of the system by less than 100 K, even at peak flux values 108 times stronger than focused sunlight. The energy quickly dissipates from the adsorbates into the surroundings in less than 5 ps, even at the highest values of photoexcitation. This surprisingly modest energy transfer of the most active regions of the plasmonic materials on the ultrafast time scale decisively proves that most plasmonic photocatalysis is not primarily thermally driven.

Nanoscale tracking plasmon-driven photocatalysis in individual nanojunctions by vibrational spectroscopy.

Plasmonic metal nanoparticles (NPs) are promising catalysts in photocatalytic reactions. Understanding the exact role of sites where two particles are approaching (hot spots) is important to achieve higher efficiency of photocatalysis, and promote the development of advanced plasmon-driven photocatalytic systems. Surface-enhanced Raman spectroscopy was employed to probe photocatalytic coupling reactions occurring at individual plasmonic nanojunctions that trap light to nanoscale while serving as nanoreactors. Compared with nanocavities fabricated using the small Ag NPs (70 nm or 82 nm), the 102 nm Ag NP-molecule-Au thin film nanojunction demonstrated enhanced reaction kinetics and catalytic efficiency. On the basis of the experimental results and theoretical modeling, it was concluded that the photochemical reaction dynamics and yields showed direct correlation with the local electric field enhancement at the nanojunction hot spot. The largely enhanced electric field generates increased hot plasmonic electrons, promoting chemical transformations of the adsorbed molecules.

Design of a scalable AuNP catalyst system for plasmon-driven photocatalysis.

In this work we present a simple, fast and cost-efficient synthesis of a metal nanoparticle catalyst on a glass support for plasmon driven heterogeneous photocatalysis. It is based on efficient mixing of metal salts as particle precursors with porous glass as the supporting material in a mixer ball mill, and the subsequent realization of a complete catalyst system by laser sintering the obtained powder on a glass plate as the support. By this, we could obtain catalyst systems with a high particle proportion and an even spatial particle distribution in a rapid process, which could be applied to various kinds of metal salt resulting in plasmon active metal nanoparticles. Furthermore, the catalyst production process presented here is easily scalable to any size of area that is to be coated. Finally, we demonstrate the catalytic performance of our catalysts by a model reaction of ethanol degradation in a self-designed lab-scale reactor.