From Plastic Waste to Green Hydrogen and Valuable Chemicals Using Sunlight and Water.

Over 79% of 6.3 billion tonnes of plastics produced from 1950 to 2015 have been disposed in lanfills or found their way to the oceans, where they will reside for up to hundreds of years before being decomposed bringing upon significant dangers to our health and ecosystems. Plastic photoreforming offers an appealing alternative by using solar energy and water to transform plastic waste into value-added chemical commodities, while simultaneously producing green hydrogen via the hydrogen evolution reaction. This review aims to provide an overview of the underlying principles of emerging plastic photoreforming technologies, highlight the challenges associated with experimental protocols and performance assessments, discuss recent global breakthroughs on the photoreforming of plastics, and propose perspectives for future research. A critical assessment of current plastic photoreforming studies shows a lack of standardised conditions, hindering comparison amongst photocatalyst performance. Guidelines to establish a more accurate evaluation of materials and systems are proposed with the aim to facilitate the translation of promising fundamental discovery in photocatalysts design.

Understanding Structure-Activity Relationship in Pt-loaded g-C3 N4 for Efficient Solar- Photoreforming of Polyethylene Terephthalate Plastic and Hydrogen Production.

Coupling the hydrogen evolution reaction with plastic waste photoreforming provides a synergistic path for simultaneous production of green hydrogen and recycling of post-consumer products, two major enablers for establishment of a circular economy. Graphitic carbon nitride (g-C3 N4 ) is a promising photocatalyst due to its suitable optoelectronic and physicochemical properties, and inexpensive fabrication. Herein, a mechanistic investigation of the structure-activity relationship of g-C3 N4 for poly(ethylene terephthalate) (PET) photoreforming is reported by carefully controlling its fabrication from a subset of earth-abundant precursors, such as dicyandiamide, melamine, urea, and thiourea. These findings reveal that melamine-derived g-C3 N4 with 3 wt.% Pt has significantly higher performance than alternative derivations, achieving a maximum hydrogen evolution rate of 7.33 mmolH2  gcat -1  h-1 , and simultaneously photoconverting PET into valuable organic products including formate, glyoxal, and acetate, with excellent stability for over 30 h of continuous production. This is attributed to the higher crystallinity and associated chemical resistance of melamine-derived g-C3 N4 , playing a major role in stabilization of its morphology and surface properties. These new insights on the role of precursors and structural properties in dictating the photoactivity of g-C3 N4 set the foundation for the further development of photocatalytic processes for combined green hydrogen production and plastic waste reforming.

Structural Engineering Three-Dimensional Nano-Heterojunction Networks for High-Performance Photochemical Sensing.

Nanoscale heterojunction networks are increasingly regarded as promising functional materials for a variety of optoelectronic and photocatalytic devices. Despite their superior charge-carrier separation efficiency, a major challenge remains in the optimization of their surface properties, with surface defects playing a major role in charge trapping and recombination. Here, we report the effective engineering of the photocatalytic properties of nanoscale heterojunction networks via deep ultraviolet photoactivation throughout their cross-section. For the first time, in-depth XPS analysis of very thick (∼10 µm) NixOy-ZnO films reveals localized p-n nanoheterojunctions with tunable oxygen vacancies (Vo) originating from both NixOy and ZnO nanocrystals. Optimizing the amount of oxygen vacancies leads to a 30-fold increase in the photochemoresistive response of these networks, enabling the detection of representative analyte concentrations down to 2 and 20 ppb at an optimal temperature of 150 °C and room temperature, respectively. Density functional theory calculations reveal that this performance enhancement is presumably due to an 80% increase in the analyte adsorption energy. This flexible nanofabrication approach in conjunction with straightforward vacancy control via photoactivation provides an effective strategy for engineering the photocatalytic activity of porous metal oxide semiconductor networks with applications in chemical sensors, photodetectors, and photoelectrochemical cells.

Optimal Coatings of Co3 O4 Anodes for Acidic Water Electrooxidation.

Implementation of proton-exchange membrane water electrolyzers for large-scale sustainable hydrogen production requires the replacement of scarce noble-metal anode electrocatalysts with low-cost alternatives. However, such earth-abundant materials often exhibit inadequate stability and/or catalytic activity at low pH, especially at high rates of the anodic oxygen evolution reaction (OER). Here, the authors explore the influence of a dielectric nanoscale-thin oxide layer, namely Al2 O3 , SiO2 , TiO2 , SnO2 , and HfO2 , prepared by atomic layer deposition, on the stability and catalytic activity of low-cost and active but insufficiently stable Co3 O4 anodes. It is demonstrated that the ALD layers improve both the stability and activity of Co3 O4 following the order of HfO2 > SnO2 > TiO2 > Al2 O3 , SiO2 . An optimal HfO2 layer thickness of 12 nm enhances the Co3 O4 anode durability by more than threefold, achieving over 42 h of continuous electrolysis at 10 mA cm-2 in 1 m H2 SO4 electrolyte. Density functional theory is used to investigate the superior performance of HfO2 , revealing a major role of the HfO2 |Co3 O4 interlayer forces in the stabilization mechanism. These insights offer a potential strategy to engineer earth-abundant materials for low-pH OER catalysts with improved performance from earth-abundant materials for efficient hydrogen production.

Understanding the Role of (W, Mo, Sb) Dopants in the Catalyst Evolution and Activity Enhancement of Co3 O4 during Water Electrolysis via In Situ Spectroelectrochemical Techniques.

Unlocking the potential of the hydrogen economy is dependent on achieving green hydrogen (H2 ) production at competitive costs. Engineering highly active and durable catalysts for both oxygen and hydrogen evolution reactions (OER and HER) from earth-abundant elements is key to decreasing costs of electrolysis, a carbon-free route for H2 production. Here, a scalable strategy to prepare doped cobalt oxide (Co3 O4 ) electrocatalysts with ultralow loading, disclosing the role of tungsten (W), molybdenum (Mo), and antimony (Sb) dopants in enhancing OER/HER activity in alkaline conditions, is reported. In situ Raman and X-ray absorption spectroscopies, and electrochemical measurements demonstrate that the dopants do not alter the reaction mechanisms but increase the bulk conductivity and density of redox active sites. As a result, the W-doped Co3 O4 electrode requires ≈390 and ≈560 mV overpotentials to reach ±10 and ±100 mA cm-2 for OER and HER, respectively, over long-term electrolysis. Furthermore, optimal Mo-doping leads to the highest OER and HER activities of 8524 and 634 A g-1 at overpotentials of 0.67 and 0.45 V, respectively. These novel insights provide directions for the effective engineering of Co3 O4 as a low-cost material for green hydrogen electrocatalysis at large scales.

Nanoscale TiO2 Coatings Improve the Stability of an Earth-Abundant Cobalt Oxide Catalyst during Acidic Water Oxidation.

The large-scale deployment of proton-exchange membrane water electrolyzers for high-throughput sustainable hydrogen production requires transition from precious noble metal anode electrocatalysts to low-cost earth-abundant materials. However, such materials are commonly insufficiently stable and/or catalytically inactive at low pH, and positive potentials required to maintain high rates of the anodic oxygen evolution reaction (OER). To address this, we explore the effects of a dielectric nanoscale-thin layer, constituted of amorphous TiO2, on the stability and electrocatalytic activity of nanostructured OER anodes based on low-cost Co3O4. We demonstrate a direct correlation between the OER performance and the thickness of the atomic layer deposited TiO2 layers. An optimal TiO2 layer thickness of 4.4 nm enhances the anode lifetime by a factor of ca. 3, achieving 80 h of continuous electrolysis at pH near zero, while preserving high OER catalytic activity of the bare Co3O4 surface. Thinner and thicker TiO2 layers decrease the stability and activity, respectively. This is attributed to the pitting of the TiO2 layer at the optimal thickness, which allows for access to the catalytically active Co3O4 surface while stabilizing it against corrosion. These insights provide directions for the engineering of active and stable composite earth-abundant materials for acidic water splitting for high-throughput hydrogen production.

Photonic Fractal Metamaterials: A Metal-Semiconductor Platform with Enhanced Volatile-Compound Sensing Performance.

Advance of photonics media is restrained by the lack of structuring techniques for the 3D fabrication of active materials with long-range periodicity. A methodology is reported for the engineering of tunable resonant photonic media with thickness exceeding the plasmonic near-field enhancement region by more than two orders of magnitude. The media architecture consists of a stochastically ordered distribution of plasmonic nanocrystals in a fractal scaffold of high-index semiconductors. This plasmonic-semiconductor fractal media supports the propagation of surface plasmons with drastically enhanced intensity over multiple length scales, overcoming the 2D limitations of established metasurface technologies. The fractal media are used for the fabrication of plasmonic optical gas sensors, achieving a limit of detection of 0.01 vol% at room temperature and sensitivity up to 1.9 nm vol%-1 , demonstrating almost a fivefold increase with respect to an optimized planar geometry. Beneficially to their implementation, the self-assembly mechanism of this fractal architecture allows fabrication of micrometer-thick media over surfaces of several square centimeters in a few seconds. The designable optical features and intrinsic scalability of these photonic fractal metamaterials provide ample opportunities for applications, bridging across transformation optics, sensing, and light harvesting.

Engineering of SnO2-Graphene Oxide Nanoheterojunctions for Selective Room-Temperature Chemical Sensing and Optoelectronic Devices.

The development of high-performing sensing materials, able to detect ppb-trace concentrations of volatile organic compounds (VOCs) at low temperatures, is required for the development of next-generation miniaturized wireless sensors. Here, we present the engineering of selective room-temperature (RT) chemical sensors, comprising highly porous tin dioxide (SnO2)-graphene oxide (GO) nanoheterojunction layouts. The optoelectronic and chemical properties of these highly porous (>90%) p-n heterojunctions were systematically investigated in terms of composition and morphologies. Optimized SnO2-GO layouts demonstrate significant potential as both visible-blind photodetectors and selective RT chemical sensors. Notably, a low GO content results in an excellent UV light responsivity (400 A W-1), with short rise and decay times, and RT high chemical sensitivity with selective detection of VOCs such as ethanol down to 100 ppb. In contrast, a high concentration of GO drastically decreases the RT response to ethanol and results in good selectivity to ethylbenzene. The feasibility of tuning the chemical selectivity of sensor response by engineering the relative amount of GO and SnO2 is a promising feature that may guide the future development of miniaturized solid-state gas sensors. Furthermore, the excellent optoelectronic properties of these SnO2-GO nanoheterojunctions may find applications in various other areas such as optoelectronic devices and (photo)electrocatalysis.

Non-Periodic Epsilon-Near-Zero Metamaterials at Visible Wavelengths for Efficient Non-Resonant Optical Sensing.

Epsilon-near-zero (ENZ) materials offer unique properties for applications including optical clocking, nonlinear optics, and telecommunication. To date, the fabrication of ENZ materials at visible wavelengths relies mostly on the use of periodic structures, providing some manufacturing and material challenges. Here, we present the engineering of nonperiodic sodium tungsten bronzes (NaxWO3) metamaterials featuring ENZ properties in the visible spectrum. We showcase their use as efficient optical sensors, demonstrating a nonresonant sensing mechanism based on refractive index matching. Our optimized ENZ metamaterials display an unconventional blue-shift of the transmittance maximum to increasing refractive index of the surrounding environment, achieving sensitivity as high as 150 nm/RIU. Our theoretical and experimental investigations provide first insights on this sensing mechanism, establishing guidelines for the future engineering and implementation of efficient ENZ sensors. The unique optoelectronic properties demonstrated by this class of tunable NaxWO3 materials bear potential for various applications ranging from light-harvesting to optical photodetectors.

One-Step Synthesis of Porous Transparent Conductive Oxides by Hierarchical Self-Assembly of Aluminum-Doped ZnO Nanoparticles.

Transparent conductive oxides (TCOs) are highly desirable for numerous applications ranging from photovoltaics to light-emitting diodes and photoelectrochemical devices. Despite progress, it remains challenging to fabricate porous TCOs (pTCOs) that may provide, for instance, a hierarchical nanostructured morphology for the separation of photoexcited hole/electron couples. Here, we present a facile process for the fabrication of porous architectures of aluminum-doped zinc oxide (AZO), a low-cost and earth-abundant transparent conductive oxide. Three-dimensional nanostructured films of AZO with tunable porosities from 10 to 98% were rapidly self-assembled from flame-made nanoparticle aerosols. Successful Al doping was confirmed by X-ray photoemission spectroscopy, high-resolution transmission electron microscopy, elemental mapping, X-ray diffraction, and Fourier transform infrared spectroscopy. An optimal Al-doping level of 1% was found to induce the highest material conductivity, while a higher amount led to partial segregation and formation of aluminum oxide domains. A controllable semiconducting to conducting behavior with a resistivity change of more than 4 orders of magnitudes from about 3 × 102 to 9.4 × 106 Ω cm was observed by increasing the AZO film porosity from 10 to 98%. While the denser AZO morphologies may find immediate application as transparent electrodes, we demonstrate that the ultraporous semiconducting layers have potential as a light-driven gas sensor, showing a high response of 1.92-1 ppm of ethanol at room temperature. We believe that these tunable porous transparent conductive oxides and their scalable fabrication method may provide a highly performing material for future optoelectronic devices.

Room-temperature photodetectors and VOC sensors based on graphene oxide-ZnO nano-heterojunctions.

The rapid development of smart wearable electronics is driving the engineering of novel miniaturized sensing materials that can rapidly respond to very small changes in the concentration of biomarkers at room temperature. Carbon-based nanomaterials offer numerous attractive properties such as low resistivity, good mechanical robustness and integration potential, but lack a strong detection and transduction mechanism for the measurement of chemical molecules or photons. Here, we present a three-dimensional nanostructured architecture comprising optimally integrated graphene oxide (GO)-ZnO heterojunctions for the room temperature sensing of volatile biomarkers. We show that this layout also provides excellent response to UV light showcasing its applicability as a visible-blind photodetector. Notably, the optimal integration of well-dispersed GO nanodomains in a 3D ZnO network significantly enhances the room-temperature chemical sensitivity and light responsivity, while higher GO contents drastically worsen the material performance. This is attributed to the different roles of GO at low and high contents. Small amounts of GO lead to the formation of electron depleted nano-heterojunctions with excellent electron-hole separation efficiency. In contrast, large amounts of GO form a percolating electrical network that inhibits the light and chemical-sensing properties of the ZnO nanoparticles. Our optimal GO-ZnO demonstrates 33 A W-1 responsivity to UV light as well as the room temperature detection of volatile organic compounds down to 100 ppb. We believe that these findings provide guidelines for the future engineering of hybrid carbon-metal oxide devices for applications extending from optoelectronics to chemical sensing and electrocatalysis.

One-Step Rapid and Scalable Flame Synthesis of Efficient WO3 Photoanodes for Water Splitting.

Photoelectrochemical water splitting is a promising approach for the carbon-free production of hydrogen using sunlight. Here, robust and efficient WO3 photoanodes for water oxidation were synthesized by the scalable one-step flame synthesis of nanoparticle aerosols and direct gas-phase deposition. Nanostructured WO3 films with tunable thickness and band gap and controllable porosity were fabricated by controlling the aerosol deposition time, concentration, and temperature. Optimal WO3 films demonstrate superior water oxidation performance, reaching a current density of 0.91 mA at 1.24 V vs. reversible hydrogen electrode (RHE) and an incident photon-to-current conversion efficiency (IPCE) of ca. 61 % at 360 nm in 0.1 m H2 SO4 . Notably, it is found that the excellent performance of these WO3 nanostructures arises from the high in situ restructuring temperature (ca. 1000 °C), which increases oxygen vacancies and decreases charge recombination at the WO3 /electrolyte interface. These findings provide a scalable approach for the fabrication of efficient photoelectrodes based on WO3 and other metal oxides for light-driven water splitting.

Facilitated ion diffusion in multiscale porous particles: application in battery separators.

Polyethylene (PE) separators have been the most popular option for commercial Li-ion batteries because of their uniform pore size, high tensile strength, low cost, and electrochemical stability. Unfortunately, PE separators generally suffer from significant dimensional changes at high temperatures, which frequently results in serious safety problems. In this regard, the integration of inorganic nanoparticles with PE separators has been considered to be a promising approach. Here, inorganic nanoparticles with a hierarchical pore structure were coated on a conventional polymer separator. The resultant composite separator exhibited superior Li ion transportation compared with separators coated with mesopore-only nanoparticles or conventional nonporous nanoparticles. The mesopores and macropores act synergistically to improve the electrolyte uptake and ionic conductivity of the inorganic nanoparticles, while other positive aspects such as their thermal and mechanical properties are still maintained.