Chemical catalytic upgrading of polyethylene terephthalate plastic waste into value-added materials, fuels and chemicals.

The substantial production of polyethylene terephthalate (PET) products, coupled with high abandonment rates, results in significant environmental pollution and resource wastage. This has prompted global attention to the development of rational strategies for PET waste treatment. In the context of renewability and sustainability, catalytic chemical technology provides an effective means to recycle and upcycle PET waste into valuable resources. In this review, we initially provide an overview of strategies employed in the thermocatalytic process to recycle PET waste into valuable carbon materials, fuels and typical refined chemicals. The effect of catalysts on the quality and quantity of specific products is highlighted. Next, we introduce the development of renewable-energy-driven electrocatalytic and photocatalytic systems for sustainable PET waste upcycling, focusing on rational catalysts, innovative catalytic system design, and corresponding underlying catalytic mechanisms. Moreover, we discuss advantages and disadvantages of three chemical catalytic strategies. Finally, existing limitations and outlook toward controllable selectivity and yield enhancement of value-added products and PET upvaluing technology for scale-up applications are proposed. This review aims to inspire the exploration of waste-to-treasure technologies for renewable-energy-driven waste management toward a circular economy.

Visible light photocatalytic bismuth oxide coatings are effective at suppressing aquatic cyanobacteria and degrading free-floating genomic DNA.

Access to safe drinking water free from microbial pollution is an issue of global concern. The use of photocatalytic thin films in water treatment has focused on titanium dioxide, which requires UV-activation, proving a potential barrier to upscaling and implementation in the real world. Visible-light-activated photocatalytic thin films, such as bismuth oxide, have recently been shown to have antimicrobial properties. However, more understanding of the photocatalytic effect on the microbial population in water is required. Glass beads coated with bismuth oxide were incubated with either Microcystis aeruginosa, Anabaena sp. or free-floating genomic DNA. The presence of bismuth oxide-coated glass beads was able to rapidly stop a population of cyanobacteria from increasing. The coated beads were also able to degrade genomic DNA. Leachate from the beads showed no increase in toxicity against human liver cells. This data demonstrates the efficacy of bismuth oxide-coated glass beads for controlling potentially dangerous cyanobacterial populations, whilst potentially reducing the amount of free-floating genomic DNA (an essential issue in the face of antimicrobial resistance) - all of which should be essential considerations in emerging water treatment technologies.

Development of a rapid method for assessing the efficacy of antibacterial photocatalytic coatings.

Visible-light activated photocatalytic coatings may represent an attractive antimicrobial solution in domains such as food, beverage, pharmaceutical, biomedical and wastewater remediation. However, testing methods to determine the antibacterial effects of photocatalytic coatings are limited and require specialist expertise. This paper describes the development of a method that enables rapid screening of coatings for photocatalytic-antibacterial activity. Relying on the ability of viable microorganisms to reduce the dye resazurin from a blue to a pink colour, the method relates the time taken to detect this colour change with number of viable microorganisms. The antibacterial activity of two photocatalytic materials (bismuth oxide and titanium dioxide) were screened against two pathogenic organisms (Escherichia coli and Klebsiella pneumoniae) that represent potential target microorganisms using traditional testing and enumeration techniques (BS ISO 27447:2009) and the novel rapid method. Bismuth oxide showed excellent antibacterial activity under ambient visible light against E. coli, but was less effective against K. pneumoniae. The rapid method showed excellent agreement with existing tests in terms of number of viable cells recovered. Due to advantages such as low cost, high throughput, and less reliance on microbiological expertise, this method is recommended for researchers seeking an inexpensive first-stage screen for putative photocatalytic-antibacterial coatings.

Magnetron Sputter-Coated Nanoparticle MoS2 Supported on Nanocarbon: A Highly Efficient Electrocatalyst toward the Hydrogen Evolution Reaction.

The design and fabrication of inexpensive highly efficient electrocatalysts for the production of hydrogen via the hydrogen evolution reaction (HER) underpin a plethora of emerging clean energy technologies. Herein, we report the fabrication of highly efficient electrocatalysts for the HER based on magnetron-sputtered MoS2 onto a nanocarbon support, termed MoS2/C. Magnetron sputtering time is explored as a function of its physiochemical composition and HER performance; increased sputtering times give rise to materials with differing compositions, i.e., Mo4+ to Mo6+ and associated S anions (sulfide, elemental, and sulfate), and improved HER outputs. An optimized sputtering time of 45 min was used to fabricate the MoS2/C material. This gave rise to an optimal HER performance with regard to its HER onset potential, achievable current, and Tafel value, which were -0.44 (vs saturated calomel electrode (SCE)), -1.45 mV s-1, and 43 mV dec-1, respectively, which has the highest composition of Mo4+ and sulfide (MoS2). Electrochemical testing toward the HER via drop casting MoS2/C upon screen-printed electrodes (SPEs) to electrically wire the nanomaterial is found to be mass coverage dependent, where the current density increases up to a critical mass (ca. 50 µg cm-2), after which a plateau is observed. To allow for a translation of the bespoke fabricated MoS2/C from laboratory to new industrial applications, MoS2/C was incorporated into the bulk ink utilized in the fabrication of SPEs (denoted as MoS2/C-SPE), thus allowing for improved electrical wiring to the MoS2/C and resulting in the production of scalable and reproducible electrocatalytic platforms. The MoS2/C-SPEs displayed far greater HER catalysis with a 450 mV reduction in the HER onset potential and a 1.70 mA cm-2 increase in the achievable current density (recorded at -0.75 V (vs SCE)), compared to a bare/unmodified graphitic SPE. The approach of using magnetron sputtering to modify carbon with MoS2 facilitates the production of mass-producible, stable, and effective electrode materials for possible use in electrolyzers, which are cost competitive to Pt and mitigate the need to use time-consuming and low-yield exfoliation techniques typically used to fabricate pristine MoS2.

Deposition of Visible Light-Active C-Doped Titania Films via Magnetron Sputtering Using CO2 as a Source of Carbon.

Doping of titanium dioxide with p-block elements is typically described as an efficient pathway for the enhancement of photocatalytic activity. However, the properties of the doped titania films depend greatly on the production method, source of doping, type of substrate, etc. The present work describes the use of pulsed direct current (pDC) magnetron sputtering for the deposition of carbon-doped titania coatings, using CO2 as the source of carbon; ratios of O2/CO2 were varied through variations of CO2 flow rates and oxygen flow control setpoints. Additionally, undoped Titanium dioxide (TiO2) coatings were prepared under identical deposition conditions for comparison purposes. Coatings were post-deposition annealed at 873 K and analysed with scanning electron microscopy (SEM), X-ray diffreaction (XRD), atomic force microscopy (AFM), and X-ray photoelectron spectroscopy (XPS). The photocatalytic properties of the thin films were evaluated under ultraviolet (UV) and visible light irradiation using methylene blue and stearic acid decomposition tests. Photoinduced hydrophilicity was assessed through measurements of the water contact angle under UV and visible light irradiation. It was found that, though C-doping resulted in improved dye degradation compared to undoped TiO2, the UV-induced photoactivity of Carbon-doped (C-doped) photocatalysts was lower for both model pollutants used.

Deposition of Visible Light Active Photocatalytic Bismuth Molybdate Thin Films by Reactive Magnetron Sputtering.

Bismuth molybdate thin films were deposited by reactive magnetron co-sputtering from two metallic targets in an argon/oxygen atmosphere, reportedly for the first time. Energy dispersive X-ray spectroscopy (EDX) analysis showed that the ratio of bismuth to molybdenum in the coatings can be effectively controlled by varying the power applied to each target. Deposited coatings were annealed in air at 673 K for 30 min. The crystalline structure was assessed by means of Raman spectroscopy and X-ray diffraction (XRD). Oxidation state information was obtained by X-ray photoelectron spectroscopy (XPS). Photodegradation of organic dyes methylene blue and rhodamine B was used for evaluation of the photocatalytic properties of the coatings under a visible light source. The photocatalytic properties of the deposited coatings were then compared to a sample of commercial titanium dioxide-based photocatalytic product. The repeatability of the dye degradation reactions and photocatalytic coating reusability are discussed. It was found that coatings with a Bi:Mo ratio of approximately 2:1 exhibited the highest photocatalytic activity of the coatings studied; its efficacy in dye photodegradation significantly outperformed a sample of commercial photocatalytic coating.

Structural formation and photocatalytic activity of magnetron sputtered titania and doped-titania coatings.

Titania and doped-titania coatings can be deposited by a wide range of techniques; this paper will concentrate on magnetron sputtering techniques, including "conventional" reactive co-sputtering from multiple metal targets and the recently introduced high power impulse magnetron sputtering (HiPIMS). The latter has been shown to deliver a relatively low thermal flux to the substrate, whilst still allowing the direct deposition of crystalline titania coatings and, therefore, offers the potential to deposit photocatalytically active titania coatings directly onto thermally sensitive substrates. The deposition of coatings via these techniques will be discussed, as will the characterisation of the coatings by XRD, SEM, EDX, optical spectroscopy, etc. The assessment of photocatalytic activity and photoactivity through the decomposition of an organic dye (methylene blue), the inactivation of E. coli microorganisms and the measurement of water contact angles will be described. The impact of different deposition technologies, doping and co-doping strategies on coating structure and activity will be also considered.