Institute of Fundamental Technological Research

Photocatalytic CO2 reduction has emerged as a promising strategy for converting solar energy into valuable chemicals, capturing the attention of scientists across various disciplines. Organic and inorganic perovskites, particularly methylammonium lead bromide (MAPbBr3), have demonstrated potential in this field due to their remarkable visible-light response and carrier transport properties. However, the catalytic performance of pristine MAPbBr3 has been limited by severe charge recombination, hindering its applicability in photocatalytic systems. Here, we show that a MAPbBr3/Bi2WO6 (MA/BWO) heterojunction significantly enhances photocatalytic CO2 reduction performance compared to individual pristine MA or BWO. This enhancement is evidenced by the superior performance of the 25% MA/BWO composite, which exhibits CO and CH4 release rates of 1.82 μmol/g/h and 0.08 μmol/g/h, respectively. This improvement is attributed to the direct Z-scheme heterojunction formed between MAPbBr3 and Bi2WO6, which facilitates efficient charge separation and suppresses charge recombination. The results challenge the previous understanding of MAPbBr3-based photocatalysts and demonstrate a novel approach for developing highly active organic and inorganic perovskite photocatalysts. The successful application of the MA/BWO heterojunction in photocatalytic CO2 reduction expands the scope of organic and inorganic perovskites in the field of renewable energy conversion. By providing a broader perspective, our findings contribute to the ongoing efforts towards sustainable energy solutions, appealing

Transparent electrodes are vital for optoelectronic devices, but their development has been constrained by the limitations of existing materials such as indium tin oxide (ITO) and newer alternatives. All face issues of robustness, flexibility,conductivity, and stability in harsh environments. Addressing this challenge, we developed a flexible, low-cost titanium nitride (TiN) nanomesh transparent electrode showcasing exceptional acid−alkali resistance. The TiN nanomesh electrode, created by depositing a TiN coating on a naturally cracked gel film substrate via a sputtering method, maintains a stable electrical performance through thousands of bending cycles. It exhibits outstanding chemical stability, resisting strong acid and alkali corrosion, which is a key hurdle for current electrodes when in contact with acidic/alkaline materials and solvents during device fabrication. This, coupled with superior light transmission and conductivity (88% at 550 nm with a sheet resistance of ∼200 Ω/sq), challenges the reliance on conventional materials. Our TiN nanomesh electrode,successfully applied in electric heaters and electrically controlled thermochromic devices, offers broad potential beyond harsh environment applications. It enables alternative possibilities for the design and fabrication of future optoelectronics for advancements in this pivotal field.

transparent electrode, titanium nitride, flexible, corrosion resistant, mesh, smart window

The integration of different precursor components to form single nanostructures via one-step synthesis process is mostly restricted by the compatibility and complexity of components. Herein, a highly uniform, spherical, hollowed, and hierarchical iron oxide-wrapped Mo–polydopamine is synthesized using a one-pot liquid-phase reaction at room temperature. Mo2C is doped with Fe3O4 to harness the rich electrons in Fe dopants for effective lowering of the unoccupied d-orbitals in Mo. The surface conductivity of the as-prepared nanostructures is enhanced by decorating them with gold nanoparticles utilizing strong interaction of Au and amine. The nanocomposites are converted into carbidic hollowed structures via an annealing process without any distortion in morphology. The well-organized structure and nanosize of the particles provide efficient catalytic performance for hydrogen evolution reaction in acidic media. MoFe–C@Au exhibits a very positive onset potential of 2 mV, low Tafel slope of 50.1 mV dec^-1, and remarkable long- term stability.

electrocatalysts,hierarchical syntheses,hydrogen evolution,molybdenum,polydopamine

Two-dimensional polystyrene sphere opals are important materials for nanotechnology applications and fundamental nanoscience research. They are a facile and inexpensive nanofabrication tool, but the quality factor of these opals has drastic differences between reports. Additives like ethanol, ions, and organic molecules in the aqueous particle spreading solution are known to affect the quality factor and growth efficiency of the produced opals. However, a systematic study on the effect and optimization of some of the most effective additives has not been reported until now. Here, we investigate the influence of additives on the growth efficiency and quality factor of such monolayers formed at the air−water interface without the use of a Langmuir−Blodgett trough. The additives induced large variations in the monolayer quality factor and growth efficiency, and we found that the ideal additive content of the spreading agents is 30 wt % < cethanol < 70 wt %, 0 < cHd 2SOd 4 < 30.5 mM, and 0 < csty < 255.0 mM. This study provides a guideline for the rational composition and additive content of the spreading solution to obtain high-quality two-dimensional opals for further applications in nanofabrication and photonics and will enable researchers and application engineers to produce standardized nanofabrication materials.

Plasma-treated polystyrene particles (PSP) are key building blocks in the fabrication of two- dimensional nanostructure arrays. Oxygen plasma etching can shrink PS particles and is a widespread tool in fundamental research and applications, but its effect has not been well understood. Here, we show that oxygen plasma induces an ultra-thin cross-linking layer on the surface of the PSPs, which increases their solvent resistance. We found in X-ray photoelectron spectroscopy (XPS) fine structure and valence band probing that the polymer C–C bonds are breaking and ecombining to form oxygenated functional groups. Our results explain, why oxygen plasma etched PS particles are more difficult to dissolve in nanofabrication procedures. Further, we used the ultra-thin crosslinked polymer layer to construct novel substrate-base microcavity arrays.

Polystyrene particle, Oxygen plasma, Cross-linking

A simple and inexpensive method for the controlled loading of silica particles with dyes and nanocrystals is presented. Polydiallyldimethylammonium chloride is used as a positively charged bridge to facilitate electrostatic adsorption of negatively charged dyes onto negatively charged silica microspheres. The particles are subsequently coated with a further silica shell to protect the dyes against chemical degradation and leakage and this shell affords a unform particle surface independent of its doping. This encapsulation method is highly versatile and can be extended to doping with semiconductor nanocrystals, which we demonstrate using CdSe/ZnS core/shell quantum dots. The synthesis steps and end products are characterized with electron microscopy, optical spectroscopy and the electrokinetic potential of the colloidal suspensions. We show that the particles adapt the optical properties of their dopants and are resistant to degradation, dopant leakage and show reasonable emission even at acidic pH values due to the protective shell.

Silica particles, Dye, Quantum dot, Polydiallyldimethylammonium chloride, Doping

The global pandemic of COVID-19 is an example of how quickly a disease-causing virus can take root and threaten our civilization. Nowadays, ultrasensitive and rapid detection of contagious pathogens is in high demand. Here, we present a novel hierarchically porous 3-dimensional magnetic molybdenum trioxide–polydopamine-gold functionalized nanosphere (3D mag-MoO3–PDA@Au NS) composed of plasmonic, semiconductor, and magnetic nanoparticles as a multifunctional nanosculptured hybrid. Based on the synthesized 3D mag-MoO3–PDA@Au NS, a universal “plug and play” biosensor for pathogens is proposed. Specifically, a magnetically-induced nanogap-enhanced Raman scattering (MINERS) detection platform was developed using the 3D nanostructure. Through a magnetic actuation process, the MINERS system overcomes Raman signal stability and reproducibility challenges for the ultrasensitive detection of SARS-CoV-2 spike protein over a wide dynamic range up to a detection limit of 10−15 g mL−1. The proposed MINERS platform will facilitate the broader use of Raman spectroscopy as a powerful analytical detection tool in diverse fields.

Enhancing the selectivity of hydrocarbon products remains a key challenge to achieving artificial energy sustainability via closing the carbon cycle. While copper-based electrodes uniquely yield hydrocarbon products, the improvement of their product selectivity through physical morphology regulation shows great potential and requires further investigation. Here, we show the distinct morphological influences of the Cu electrode on the reaction selectivity. We synthesize binder-free, vertically aligned, nanoid forest-like copper electrocatalysts for superior improved methane conversion selectivity with respect to planar Cu. These Cu nanocomposites are fabricated through the conformal coating of vertically aligned multiwalled carbon nanotube array electrodes, which have matured to a cost-effective and scalable technology over the past two decades. Simulations reveal that carbon intermediates and protons can be confined in the gaps of the nanoid copper forest, which are formed in situ and in turn cover the catalytic sites and facilitate the simultaneous transfer of coupled electrons and protons. Such forest-like antenna morphology benefits from a threefold improvement of the CO2 electroreduction performance through a decreased reaction onset potential, an increased current density, and enhanced hydrocarbon selectivity.

CO2 conversion,electroreduction,MWCNT,copper catalyst

Chains of alternating semiconductor nanocrystals are complex nanostructures that can offer control over photogenerated charge carriers dynamics and quantized electronic states. We develop a simple one-pot colloidal synthesis of complex Cu1.94S-CdS and Cu1.94S-ZnS nanochains exploiting an equilibrium driving ion exchange mechanism. The chain length of the heterostructures can be tuned using a concentration dependent cation exchange mechanism controlled by the precursor concentrations, which enables the synthesis of monodisperse and uniform Cu1.94S-CdS-Cu1.94S nanochains featuring three epitaxial junctions. These seamless junctions enable efficient separation of photogenerated charge carriers, which can be harvested for photocatalytic applications. We demonstrate the superior photocatalytic activity of these noble metal free materials through solar hydrogen generation at a hydrogen evolution rate of 22.01 mmol g–1 h–1, which is 1.5-fold that of Pt/CdS heterostructure photocatalyst particles.

Colloidal synthesis of photocatalysts with potential to overcome the drawback of low photocatalytic efficiency brought by charge recombination and narrow photo-response has been a challenge. Herein, a general and facile colloidal approach to synthesize orthorhombic phase Bi2S3 particles with rod and flower-like morphology is reported. We elucidate the formation and growth process mechanisms of these synthesized nanocrystals in detail and cooperate these Bi2S3 particles with metallic gold nanoparticles (AuNPs) to construct heterostructured photocatalysts. The unique properties of AuNPs featuring tunable surface plasmon resonance and large field enhancement are used to sensitize the photocatalytic activity of the Bi2S3 semiconductor particles. The morphology, structure, elemental composition, and light absorption ability of the prepared catalysts are characterized by (high-resolution) transmission electron microscopy, scanning electron microscopy, X-ray diffraction spectroscopy, X-ray photoelectron spectroscopy, and UV–vis absorption spectroscopy. The catalysts exhibit high and stable photocatalytic activity for the degradation of organic pollutants demonstrated using rhodamine B and methyl orange dyes under solar light irradiation. We show that the incorporation of the AuNPs with the Bi2S3 particles increases the photocatalytic activity 1.2 to 3-fold. Radical trapping analysis indicates that the production of hydroxyl and superoxide radicals are the dominant active species responsible for the photodegradation activity. The photocatalysts exhibit good stability and recyclability.

Bi2S3, nanoflower, nanorod, photocatalysis, heterostructures, AuNPs

Until now, the growth of periodic vertically aligned multi-walled carbon nanotube (VA-
MWCNT) arrays was dependent on at least one lithography step during fabrication. Here, we demonstrate a lithography-free fabrication method to grow hexagonal arrays of self-standing VA-MWCNTs with tunable pitch and MWCNT size. The MWCNTs are synthesized by plasma enhanced chemical vapor deposition (PECVD) from Ni catalyst particles. Template guided dewetting of a thin Ni film on a hexagonally close-packed silica particle monolayer provides periodically distributed Ni catalyst particles as seeds for the growth of the periodic MWCNT arrays. The diameter of the silica particles directly controls the pitch of the periodic VA-MWCNT arrays from 600 nm to as small as 160 nm. The diameter and length of the individual MWCNTs can also be readily adjusted and are a function of the Ni particle size and PECVD time. This unique method of lithography-free growth of periodic VA-MWCNT arrays can be utilized for the fabrication of large-scale biomimetic materials

periodic, ithography free, nanofabrication, template guided, vertically-aligned multi- walled carbon nanotubes, self-standing

Melanin nanoparticles are known to be biologically benign to human cells for a wide range of concentrations in a high glucose culture nutrition. Here, we show cytotoxic behavior at high nanoparticle and low glucose concentrations, as well as at low nanoparticle concentration under exposure to (nonionizing) visible radiation. To study these effects in detail, we developed highly monodispersed melanin nanoparticles (both uncoated and glucose-coated). In order to study the effect of significant cellular uptake of these nanoparticles, we employed three cancer cell lines: VM-M3, A375 (derived from melanoma), and HeLa, all known to exhibit strong macrophagic character, i.e., strong nanoparticle uptake through phagocytic ingestion. Our main observations are: (i) metastatic VM-M3 cancer cells massively ingest melanin nanoparticles (mNPs); (ii) the observed ingestion is enhanced by coating mNPs with glucose; (iii) after a certain level of mNP ingestion, the metastatic cancer cells studied here are observed to die—glucose coating appears to slow that process; (iv) cells that accumulate mNPs are much more susceptible to killing by laser illumination than cells that do not accumulate mNPs; and (v) non-metastatic VM-NM1 cancer cells also studied in this work do not ingest the mNPs, and remain unaffected after receiving identical optical energy levels and doses. Results of this study could lead to the development of a therapy for control of metastatic stages of cancer.

melanoma, melanin nanoparticles, cytotoxicity, laser medical applications, hyperthermia

Nanonail shaped ZnS-CuS-Bi three component nanoparticles are synthesized via a simple one-pot colloidal
synthesis route by thermal decomposition of metal-thiolate precursors. A thiol serves as the sulfur source and a
phase directing capping agent promotes selective anisotropic growth of the nanocrystals in a noncoordinating
solvent. After the nucleation and growth of a CuS rod, reactive Cu ions serve as catalytic seeds for the nucleation
and growth of ZnS and Bi at the CuS nanorod tips. Thereby the obtained ZnS-CuS-Bi nanocrystals form a chain of
two semiconductors of decreasing band gap and a metallic Bi nanoparticle. The three components absorb light in
different spectral regions enabling efficient light harvesting. Furthermore, the band edge alignment of ZnS and
CuS promote photogenerated electron funneling towards the Bi catalyst particle, which promotes charge carrier
separation, effectively channeling the catalytic activity. The photocatalytic performance is assessed at the
example of the photodegradation of the organic dye Rhodamine B, and shows excellent performance rendering
these nanonails as inexpensive, non-toxic and efficient photocatalyst to remedy environmental pollution

We propose a simple and inexpensive SiO2 submicron particle synthesis method based on a PTFE helical capillary microreactor. The device is based on Dean flow mediated, ultrafast mixing of two liquid phases in a microfluidic spiral pipe. Excellent control of particle size between 100 nm and 600 nm and narrow polydispersity can be achieved by controlling the device and process parameters. Numerical simulations are performed to determine the optimal device dimensions. In the mother liquor the silica particles exhibit zeta potentials < -60 mV, rendering them very stable even at high particle volume fractions. The current device typically produces around 0.234 g/h of the silica particles.

SiO2 particle synthesis, continuous flow synthesis, helical capillary microreactor

Ultrasensitive sensors of various physical properties can be based on percolation systems, e.g., insulating media filled with nearly touching conducting particles. Such a system at its percolation threshold featuring the critical particle concentration, changes drastically its response (electrical conduction, light transmission, etc.) when subjected to an external stimulus. Due to the critical nature of this threshold, a given state at the threshold is typically very unstable. However, stability can be restored without significantly sacrificing the structure sensitivity by forming weak connections between the conducting particles. In this work, we employed nano-bridged nanosphere lithography to produce such a weakly connected percolation system. It consists of two coupled quasi-Babinet complementary arrays, one with weakly connected, and the other with disconnected metallic islands. We demonstrate via experiment and simulation that the physics of this plasmonic system is non-trivial, and leads to the extraordinary optical transmission at narrowly defined peaks sensitive to system parameters, with surface plasmons mediating this process. Thus, our system is a potential candidate for percolation effect based sensor applications. Promising detection schemes could be based on these effects.

New semiconducting metal oxides of various compositions are of great interest for efficient solar water oxidation. In this report, Mo-doped SnO2 (Mo:SnO2) thin films deposited by reactive magnetron co-sputtering in the Ar and O2 gas environment are studied. The Sn to Mo ratio in the films can be controlled by changing the O2 partial pressure and the deposition power of the Sn and Mo targets. Increasing the Mo concentration in the film leads to the increase in the oxygen vacancy density, which limits the maximum achievable photocurrent density. The thin films exhibit a direct band gap of 2.7 eV, the maximum achievable photocurrent density of 0.6 mA cm^−2 at 0 VRHE and the onset potential of 0.14 VRHE. The incident photon to current transfer (IPCE) efficiency of 22% is shown at a 450 nm wavelength. The initial performance of the Mo:SnO2 thin films is evaluated for solar water oxidation.

Mo:SnO2, thin films, photoanode, photocurrent density, Sn/mo ratio, band gap

Semiconducting ternary metal oxide thin films exhibit a promising application for solarenergy conversion. However, the efficiency of the conversion is still limited by a band gapof a emiconductor, which determines an obtainable internal photovoltage for solar watersplitting. In this report the tunability of the tin tungstate band gap by O2 partial pressurecontrol in the magnetron co-sputtering process is shown. A deficiency in the Sn concentration increases the optical band gap of tin ungstate thin films. The optimum band gap of 1.7 eV for tin tungstate films is achieved for a Sn to W ratio at unity, which establishes thehighest photoelectrochemical activity. In particular, a maximum photocurrent density of 0.375 mA cm^2 at 1.23 VRHE and the lowest reported onset potential of -0.24 VRHE for SnWO4 thin films without any co-catalyst are achieved. Finally, we demonstrate that a Ni protection layer on the SnWO4 thin film enhances the photoelectrochemical stability, which isof paramount importance for application.

thin film, tin tungstate, reactive magnetron sputtering, photocurrent density, thickness band gap

We develop nano-bridged nanosphere lithography (NB-NSL), a modification to the widely used conventional nanosphere lithography (NSL). Nano-bridges between polystyrene (PS) spheres of a pristine NSL template are controllably formed in a two-step process: (i) spin-coating of a dilute styrene solution on top of the template, followed by (ii) oxygen plasma etching of the template. We show that the nanobridge dimensions can be precisely tuned by controlling the pre-processing conditions and the plasma etching time. The resulting lithography templates feature control over the shape and size of the apertures, which determine the morphology of the final nano-island arrays after material deposition and template removal. The unique advantage of NB-NSL is that PS particle templates based on a single PS particle diameter can be utilized for the fabrication of a variation of nano-island shapes and sizes, whereas conventional NSL yields only bowtie-shaped nano-islands, with their size being predetermined by the PS particle diameter of the template.

nanofabrication, nanosphere lithography, colloid lithography

There is an urgent need for new materials that can catalyze or drive the photoelectrochemical (PEC) conversion of solar energy into chemical energy, i.e. solar fuels. Copper bismuth oxide (CBO) is a promising photocathode material for the photochemical reduction of water. Here, we systematically control the stoichiometry of CBO thin films prepared by reactive, direct-current magnetron co-sputtering from metallic Bi and Cu targets. The intrinsic photophysical and PEC material properties are investigated and evaluated in order to determine the optimum composition for hydrogen formation. Changing the stoichiometry of the films reveals a dramatic change in the optical band gap and crystal structure of CBO. The largest photocurrent density was achieved for a copper-to-bismuth ion ratio of 0.53, close to the CuBi2O4 stoichiometry, which yielded Jph = − 0.48 mA cm^−2 at 0 VRHE (RHE = reversible hydrogen electrode). This is the highest value to date for the photochemical reduction of water with CuBi2O4 without an externally applied bias. The absorbed photon-to-current efficiency and the photostability of the films in neutral and alkaline electrolytes were also investigated.

CuBi2O4, copper bismuth oxide, water reduction, water splitting, photocathode, magnetron sputtering

A plasmonic structure with transmission highly tunable in the mid-infrared spectra range is developed. This structure consists of a hexagonal array of metallic discs located on top of silicon pillars protruding through holes in a metallic Babinet complementary film. We reveal with FDTD simulations that changing the hole diameter tunes the main plasmonic resonance frequency of this structure throughout the infrared range. Due to the underlying Babinet physics of these coupled arrays, the spectral width of these plasmonic resonances is strongly reduced, and the higher harmonics are suppressed. Furthermore, we demonstrate that this structure can be easily produced by a combination of the nanosphere lithography and the metal-assisted chemical etching technique.