Solar reforming as an emerging technology for circular chemical industries.

The adverse environmental impacts of greenhouse gas emissions and persistent waste accumulation are driving the demand for sustainable approaches to clean-energy production and waste recycling. By coupling the thermodynamically favourable oxidation of waste-derived organic carbon streams with fuel-forming reduction reactions suitable for producing clean hydrogen or converting CO2 to fuels, solar reforming simultaneously valorizes waste and generates useful chemical products. With appropriate light harvesting, catalyst design, device configurations and waste pre-treatment strategies, a range of sustainable fuels and value-added chemicals can already be selectively produced from diverse waste feedstocks, including biomass and plastics, demonstrating the potential of solar-powered upcycling plants. This Review highlights solar reforming as an emerging technology that is currently transitioning from fundamental research towards practical application. We investigate the chemistry and compatibility of waste pre-treatment, introduce process classifications, explore the mechanisms of different solar reforming technologies, and suggest appropriate concepts, metrics and pathways for various deployment scenarios in a net-zero-carbon future.

Floating Carbon Nitride Composites for Practical Solar Reforming of Pre-Treated Wastes to Hydrogen Gas.

Solar reforming (SR) is a promising green-energy technology that can use sunlight to mitigate biomass and plastic waste while producing hydrogen gas at ambient pressure and temperature. However, practical challenges, including photocatalyst lifetime, recyclability, and low production rates in turbid waste suspensions, limit SR's industrial potential. By immobilizing SR catalyst materials (carbon nitride/platinum; CNx |Pt and carbon nitride/nickel phosphide; CNx |Ni2 P) on hollow glass microspheres (HGM), which act as floating supports enabling practical composite recycling, such limitations can be overcome. Substrates derived from plastic and biomass, including poly(ethylene terephthalate) (PET) and cellulose, are reformed by floating SR composites, which are reused for up to ten consecutive cycles under realistic, vertical simulated solar irradiation (AM1.5G), reaching activities of 1333 ± 240 µmolH2 m-2 h-1 on pre-treated PET. Floating SR composites are also advantageous in realistic waste where turbidity prevents light absorption by non-floating catalyst powders, achieving 338.1 ± 1.1 µmolH2 m-2 h-1 using floating CNx versus non-detectable H2 production with non-floating CNx and a pre-treated PET bottle as substrate. Low Pt loadings (0.033 ± 0.0013% m/m) demonstrate consistent performance and recyclability, allowing efficient use of precious metals for SR hydrogen production from waste substrates at large areal scale (217 cm2 ), taking an important step toward practical SR implementation.

Comproportionation of CO2 and Cellulose to Formate Using a Floating Semiconductor-Enzyme Photoreforming Catalyst.

Formate production via both CO2 reduction and cellulose oxidation in a solar-driven process is achieved by a semi-artificial biohybrid photocatalyst consisting of immobilized formate dehydrogenase on titanium dioxide (TiO2 |FDH) producing up to 1.16±0.04 mmolformate g TiO 2 ${{_{\ {\rm TiO}{_{2}}}}}$ -1 in 24 hours at 30 °C and 101 kPa under anaerobic conditions. Isotopic labeling experiments with 13 C-labeled substrates support the mechanism of stoichiometric formate formation through both redox half-reactions. TiO2 |FDH was further immobilized on hollow glass microspheres to perform more practical floating photoreforming allowing vertical solar light illumination with optimal light exposure of the photocatalyst to real sunlight. Enzymatic cellulose depolymerization coupled to the floating photoreforming catalyst generates 0.36±0.04 mmolformate per m2 irradiation area after 24 hours. This work demonstrates the synergistic solar-driven valorization of solid and gaseous waste streams using a biohybrid photoreforming catalyst in aqueous solution and will thus provide inspiration for the development of future semi-artificial waste-to-chemical conversion strategies.

Transport and targeted binding of Pluronic-coated nanoparticles in unsaturated porous media.

The effectiveness of most in situ remedial technologies, including nanoremediation, lies on successful delivery of reagents to a subsurface target treatment zone. Targeted delivery of engineered nanoparticles (NPs) to treat petroleum hydrocarbons present in the unsaturated zone requires an understanding of their transport behaviour in these systems. A series of column experiments explored the effect of initial water saturation, flowrate, input dosage, and porous medium texture on the transport of iron oxide or cobalt ferrite NPs coated with an amphiphilic co-polymer, as well as their targeted attachment to a crude oil zone. As the initial water content increased with a concomitant reduction in air saturation, the degree of tailing present in the NP breakthrough curves (BTCs) reduced, and the mass of NPs recovered increased. Air saturation is positively correlated with the magnitude of air-water interfaces, which provide additional NP retention sites. At a lower injection flow rate, NP retention increased due to a longer residence time and comparatively high air saturation. NP transport behaviour was not sensitive to NP injection dose over the range tested. Increased retention and retardation of the NP BTC was observed in sediments with a higher clay and silt content. NPs coated with a lower concentration of a Pluronic block co-polymer to promote binding were preferentially retained within the crude oil zone. To simulate the asymmetrical NP breakthrough curves observed from the unsaturated systems required the use of a model that accounted for both mobile and immobile flow regions as well as NP attachment and detachment with nonlinear Langmuirian blocking. This model allowed examination of attachment and detachment rate coefficients which captured NP interaction with the porous medium and/or crude oil. It was found that the initial water saturation and flow rate did not have an appreciable impact on the NP attachment rate coefficient, while it increased by ~10× with increasing clay and silt content, and by ~100× in the presence of crude oil, indicating preferential NP attachment within the crude oil zone. As a result of the lower NP polymer concentration coating used to promote increased attachment to crude oil, higher retention was observed near the column inlet and was captured quantitatively by adding a depth-dependent straining term to the model. This retention behaviour represents a combination of irreversible attachment at the air-water interfaces and straining near the column inlet enhanced by the formation of NP aggregates. The detachment rate coefficient decreased with a lower initial water saturation and flowrate, but increased with higher clay and silt content. The findings from this study contribute to our understanding of the transport and binding behaviour of Pluronic-coated NPs in unsaturated conditions and, in particular, the role of initial water content, flowrate and porous medium texture. Demonstrated delivery of NPs to a target zone is an important step towards expanding the utility of NPs as treatment reagents.

Spatiotemporal geo-electrical sensing of a Pluronic-coated cobalt ferrite nanoparticle slug in natural sand flow-through columns.

Rising industrial interest in the application of nanomaterials for the remediation of contaminated sites has led to concern over the environmental fate of the nanoremediation agents used. A critical requirement in evaluating and understanding nanoparticle (NP) behaviour in porous media is the development of analytical methods capable of in situ monitoring of complex NP transport dynamics. Spectral induced polarization (SIP), a non-invasive geo-electrical technique, offers a promising tool for detecting and quantifying NPs in soil and aquifer media. However, its application for monitoring the spatial migration and attachment behaviour of NPs remains uninvestigated. Here, we present results from flow-through experiments where we monitored the transport of cobalt ferrite nanoparticles (CoFe-NPs) coated with Pluronic, an amphiphilic polymer, in natural aquifer sand columns. We coupled concentration breakthrough curve analysis with SIP monitoring and reactive transport modeling to relate spatiotemporal NP concentration distributions to geo-electrical signals. Changes in the real (σ') conductivity at three different locations along the columns closely correlated with model-computed total (solid plus aqueous phase) NP concentrations during the propagation of a NP slug. The imaginary conductivity (σ″) correlated closely with the arrival of the NP-slug. However, during the receding front, bimodal σ″-signal peak behaviour was observed propagating through the columns, indicating the existence of complex in situ NP transport dynamics, potentially revealing the rupture of nanoclusters upon straining and their effect on bulk charge storage that may not be obvious from breakthrough curve data alone. Fitting of a double Cole-Cole relaxation model yielded distinct shifts in relaxation time (τ) associated with the polarization of smaller length-scale particles. Post-NP pulse τ and σ″ did not return to pre-injection values; these lingering signals were caused by retained NP concentrations as low as 8.8 mg kg-1. Our results support the applicability of SIP for spatial and temporal monitoring of NP distributions, with implications for the investigation of NP transport and nanoremediation strategies.

Factors affecting pluronic-coated iron oxide nanoparticle binding to petroleum hydrocarbon-impacted sediments.

Effective targeted delivery of nanoparticle agents may enhance the remediation of soils and site characterization efforts. Nanoparticles coated with Pluronic, an amphiphilic block co-polymer, demonstrated targeted binding behaviour toward light non-aqueous phase liquids such as heavy crude oil. Various factors including coating concentration, oil concentration, oil type, temperature, and pH were assessed to determine their effect on nanoparticle binding to heavy crude oil-impacted sandy aquifer material. Nanoparticle binding was increased by decreasing the coating concentration, increasing oil concentration, using heavier oil types, and increasing temperature, while pH over the range of 5-9 was found to have no effect. Nanoparticle transport and binding in columns packed with clean and oily porous media demonstrated the ability for efficient nanoparticle targeted binding. For the conditions explored, the attachment rate coefficient in columns packed with clean sand was 2.10 ± 0.66 × 10-4 s-1; however, for columns packed with oil-impacted sand a minimum attachment rate coefficient of 8.86 ± 0.43 × 10-4 s-1 was estimated. The higher attachment rate for the oil-impacted sand system indicates that nanoparticles may preferentially accumulate to oil-impacted zones present at heterogeneous impacted sites. Simulations were used to demonstrate this hypothesis using the set of parameters generated in this effort. This work contributes to our understanding of the application conditions that are required for efficient targeted binding of nanoparticles to crude-oil impacted porous media.

Targeted nanoparticle binding & detection in petroleum hydrocarbon impacted porous media.

Targeted nanoparticle binding has become a core feature of experimental pharmaceutical product design which enables more efficient payload delivery and enhances medical imaging by accumulating nanoparticles in specific tissues. Environmental remediation and geophysical monitoring encounter similar challenges which may be addressed in part by the adoption of targeted nanoparticle binding strategies. This study illustrates that engineered nanoparticles can bind to crude oil-impacted silica sand, a selective adsorption driven by active targeting based on an amphiphilic polymer coating. This coating strategy resulted in 2 mg/kg attachment to clean silica sand compared to 8 mg/kg attachment to oil-impacted silica sand. It was also shown that modifying the surface coating influenced the binding behaviour of the engineered nanoparticles - more hydrophobic polymers resulted in increased binding. Successful targeting of Pluronic-coated iron oxide nanoparticles to a crude oil and silica sand mixture was demonstrated through a combined quantitative Orbital Emission Spectroscopy mass analysis supported by Vibrating Scanning Magnetometer magnetometry, and a qualitative X-ray micro-computed tomography (CT) visualization approach. These non-destructive characterization techniques facilitated efficient analysis of nanoparticles in porous medium samples with minimal sample preparation, and in the case of X-Ray CT, illustrated how targeted nanoparticle binding may be used to produce 3-D images of contaminated porous media. This work demonstrated successful implementation of nanoparticle targeted binding toward viscous LNAPL such as crude oil in the presence of a porous medium, a step which opens the door to successful application of targeted delivery technology in environmental remediation and monitoring.

Sensing Coated Iron-Oxide Nanoparticles with Spectral Induced Polarization (SIP): Experiments in Natural Sand Packed Flow-Through Columns.

The development of nanoparticle-based soil remediation techniques is hindered by the lack of accurate in situ nanoparticle (NP) monitoring and characterization methods. Spectral induced polarization (SIP), a noninvasive geophysical technique, offers a promising approach to detect and quantify NPs in porous media. However, its successful implementation as a monitoring tool requires an understanding of the polarization mechanisms, the governing NP-associated SIP responses and their dependence on the stabilizing coatings that are typically used for NPs deployed in environmental applications. Herein, we present SIP responses (0.1-10 000 Hz) measured during injection of a poloxamer-coated superparamagnetic iron-oxide nanoparticle (SPION) suspension in flow-through columns packed with natural sand from the Borden aquifer. An advective-dispersive transport model is fitted to outflow SPION concentration measurements to compute average concentrations over the SIP spatial response domain (within the columns). The average SPION concentrations are compared with the real and imaginary components of the complex conductivity. Excellent correspondence is found between the average SPION concentrations in the columns and the imaginary conductivity values, suggesting that NP-mediated polarization (that is, charge storage) increases proportionally with increasing SPION concentration. Our results support the possibility of SIP monitoring of spatial and temporal NP distributions, which can be immediately deployed in bench-scale studies with the prospect of future real-world field applications.

Solar photocatalytic degradation of naphthenic acids in oil sands process-affected water.

Bitumen mining in the Canadian oil sands creates large volumes of oil sands process-affected water (OSPW), the toxicity of which is due in part to naphthenic acids (NAs) and other acid extractable organics (AEO). The objective of this work was to evaluate the potential of solar photocatalysis over TiO2 to remove AEO from OSPW. One day of photocatalytic treatment under natural sunlight (25 MJ/m(2) over ∼14 h daylight) eradicated AEO from raw OSPW, and acute toxicity of the OSPW toward Vibrio fischeri was eliminated. Nearly complete mineralization of organic carbon was achieved within 1-7 day equivalents of sunlight exposure, and degradation was shown to proceed through a superoxide-mediated oxidation pathway. High resolution mass spectrometry (HRMS) analysis of oxidized intermediate compounds indicated preferential degradation of the heavier and more cyclic NAs (higher number of double bond equivalents), which are the most environmentally persistent fractions. The photocatalyst was shown to be recyclable for multiple uses, and thus solar photocatalysis may be a promising "green" advanced oxidation process (AOP) for OSPW treatment.

Recyclable graphene oxide-supported titanium dioxide photocatalysts with tunable properties.

A modular synthesis technique was developed for producing graphene-supported titanium dioxide photocatalysts. The modular synthesis allowed for simple tuning of the ratio of particle loading on the graphene oxide (GO) surface as well as good photocatalytic activity of the composite and quick, efficient magnetic separability. GO flakes were used as a support for titanium dioxide nanoparticles and SiO2 insulated nano-sized magnetite aggregates. Different composition ratios were tested, resulting in a catalyst formulation with photocatalytic activity exceeding that of a commercial photocatalyst by a factor of 1.2 as well as excellent recyclability, with the capability to degrade 3 mg/L methylene blue in aqueous solution over 10 consecutive trials with minimal loss in photocatalytic efficiency. Recovery of the catalyst was achieved by simply exposing the nanocomposite to a magnetic field for ∼1 minute. Furthermore, it was found that the catalyst could be regenerated to its initial efficiency through simple UV treatment to provide additional re-use. To highlight the importance of the nanocomposite to the current water treatment industry, we showed rapid degradation of pharmaceutical compounds caffeine and carbamazepine within 60 min. The nanocomposite shows activity exceeding that of commercial photocatalyst P25 with the added benefit of being fully recoverable, reusable, and easy to produce. Overall, a simple technique for producing and tuning an effective magnetically recyclable nanocomposite was developed which should allow easy scalability and industrial production, a factor critical for the implementation of nano-based water treatment techniques.

Mesoporous magnetically recyclable photocatalysts for water treatment.

Photocatalysis over titanium dioxide is a promising technology for water purification and degradation of emerging contaminants, however, catalyst efficiency and recovery after the photocatalytic reaction are key challenges that have limited the practical deployment of TiO2 in water treatment applications. Herein we report the synthesis of core-shell, superparamagnetic gamma-Fe2O3@SiO2@TiO2 colloidal nanospheres with a mesoporous TiO2 shell, their characterization, and application in photocatalysis. The final surface area of the particles was - 100 m2 g(-1), and their photocatalytic efficiency matched that of P25 TiO2.

Synthesis of magnetic rattle-type nanostructures for use in water treatment.

A hydrothermal technique to simultaneously remove a SiO2 template and crystallize a TiO2 outer layer was used to create magnetically separable, hollow rattle-type nanoparticles consisting of a magnetic Fe3O4 core contained within a hollow TiO2 shell. Fe3O4 cores approximately 240 nm in diameter were synthesized, subsequently coated by SiO2 and finally coated with TiO2. This was followed by a hydrothermal treatment to selectively etch the silica, resulting in rattle-type particles with a final outer shell diameter of approximately 390 nm. The product of hydrothermal treatment were rattle-type particles with increased crystallinity and a 68% increase in surface area. Characterization confirmed the ability to etch a hard SiO2 template through use of a simple and benign thermal treatment with pure water, while simultaneously introducing a crystalline phase into the TiO2 active layer. The potential of the particles to be employed as a catalyst in UV induced advanced water treatment for removal of organic contaminants was evaluated through a colorimetric photocatalytic degradation assay using methylene blue as a model contaminant. The ability of the particles to be magnetically separated from solution after treatment and recycled for consecutive treatment cycles was then demonstrated. This technique for selectively removing a hard SiO2 template while simultaneously crystallizing a TiO2 shell avoids the use of hazardous chemical etchants or complex processing, rendering the synthesis of hierarchical, multimaterial, hollow, porous rattle-type particles a simple, attractive, and environmentally friendly "one-pot" technique for potential industrial application.

Mesoporous hollow sphere titanium dioxide photocatalysts through hydrothermal silica etching.

Robust, monodisperse, mesoporous titanium dioxide (TiO2) submicrometer hollow spheres were synthesized through a single step hydrothermal silica etching reaction under mild conditions. Efficient silica (SiO2) removal was achieved without the use of toxic reagents, and a unique controllable silica redeposition mechanism was identified, imparting the hollow spheres with excellent structural integrity. The parameters of the hydrothermal reaction affecting the etching process, including pH, temperature, and silica concentration, were systematically investigated and optimized for the production of silica-templated hollow structures. The resulting processing conditions yielded TiO2 hollow spheres with a surface area of ∼300 m² g⁻¹ and anatase phase crystallization, which exhibited high adsorption capacity for methylene blue dye and good photocatalytic activity without requiring high-temperature calcination.