Surface Area-Enhanced Cerium and Sulfur-Modified Hierarchical Bismuth Oxide Nanosheets for Electrochemical Carbon Dioxide Reduction to Formate.

Electrochemical carbon dioxide reduction reaction (ECO2RR) is a promising approach to synthesize fuels and value-added chemical feedstocks while reducing atmospheric CO2 levels. Here, high surface area cerium and sulfur-doped hierarchical bismuth oxide nanosheets (Ce@S-Bi2O3) are develpoed by a solvothermal method. The resulting Ce@S-Bi2O3 electrocatalyst shows a maximum formate Faradaic efficiency (FE) of 92.5% and a current density of 42.09 mA cm-2 at -1.16 V versus RHE using a traditional H-cell system. Furthermore, using a three-chamber gas diffusion electrode (GDE) reactor, a maximum formate FE of 85% is achieved in a wide range of applied potentials (-0.86 to -1.36 V vs RHE) using Ce@S-Bi2O3. The density functional theory (DFT) results show that doping of Ce and S in Bi2O3 enhances formate production by weakening the OH* and H* species. Moreover, DFT calculations reveal that *OCHO is a dominant pathway on Ce@S-Bi2O3 that leads to efficient formate production. This study opens up new avenues for designing metal and element-doped electrocatalysts to improve the catalytic activity and selectivity for ECO2RR.

Elucidating Sensitivity and Stability Relationship of Gold-Carbon Hybrid LSPR Sensors Using Principal Component Analysis.

Sensitive localized surface plasmon resonance (LSPR) sensing is achieved using nanostructured geometries of noble metals which typically have dimensions less than 100 nm. Among the plethora of geometries and materials, the spherical geometries of gold (Au) are widely used to develop sensitive bio/chemical sensors due to ease of manufacturing and biofunctionlization. One major limitation of spherical-shaped geometries of Au, used for LSPR sensing, is their low refractive index (RI) sensitivity which is commonly addressed by adding another material to the Au nanostructures. However, the process of addition of new material on Au nanostructures, while retaining the LSPR of Au, often comes with a trade-off which is associated with the instability of the developed composite, especially in harsh chemical environments. Addressing this challenge, we develop a Au-graphene-layered hybrid (Au-G) with high stability (studied up to 2 weeks here) and enhanced RI sensitivity (a maximum of 180.1 nm/RIU) for generic LSPR sensing applications using spherical Au nanostructures in harsh chemical environments, involving organic solvents. Additionally, by virtue of principal component analysis, we correlate stability and sensitivity of the developed system. The relationship suggests that the shelf life of the material is proportional to its sensitivity, while the stability of the sensor during the measurement in liquid environment decreases when the sensitivity of the material is increased. Though we uncover this relationship for the LSPR sensor, it remains evasive to explore similar relationships within other optical and electrochemical transduction techniques. Therefore, our work serves as a benchmark report in understanding/establishing new correlations between sensing parameters.

Nanoplasmonic biosensor for rapid detection of multiple viral variants in human serum.

As viruses constantly change due to mutation, variants are expected to emerge demanding development of sensors capable of detecting multiple variants using one single sensor platform. Herein, we report the integration of a synthetic binder against SARS-CoV-2 with a nanoplasmonic-based sensing technology, which enables the successful detection of spike proteins of Alpha, Beta and Gamma variants of SARS CoV-2. The recognition event is achieved by specific nanostructured molecularly imprinted polymers (nanoMIPs), developed against a region of the receptor binding domain (RBD) of the SARS CoV-2 spike protein. The transduction is based on the principle of localized surface plasmon resonance (LSPR) associated with silver nanostructures. The nanoMIPs-functionalised LSPR sensor allows for the detection of all 3 protein variants with a limit of detection of 9.71 fM, 7.32 fM and 8.81 pM using wavelength shifts respectively for Alpha, Beta and Gamma spike protein variants. This can be achieved within 30 min from the sample collection, both from blood and using nasal swab, thus making this sensor suitable for rapid detection of COVID-19. Additionally, the turnaround time for sensor development and validation can be completed in less than 8 weeks, making it suitable for addressing future pandemic needs without the requirement for biological binding agents, which is one of the bottlenecks to the supply chain in diagnostic devices.

Doping Independent Work Function and Stable Band Gap of Spinel Ferrites with Tunable Plasmonic and Magnetic Properties.

Tuning optical or magnetic properties of nanoparticles, by addition of impurities, for specific applications is usually achieved at the cost of band gap and work function reduction. Additionally, conventional strategies to develop nanoparticles with a large band gap also encounter problems of phase separation and poor crystallinity at high alloying degree. Addressing the aforementioned trade-offs, here we report Ni-Zn nanoferrites with energy band gap (Eg) of ≈3.20 eV and a work function of ≈5.88 eV. While changes in the magnetoplasmonic properties of the Ni-Zn ferrite were successfully achieved with the incorporation of bismuth ions at different concentrations, there was no alteration of the band gap and work function in the developed Ni-Zn ferrite. This suggests that with the addition of minute impurities to ferrites, independent of their changes in the band gap and work function, one can tune their magnetic and optical properties, which is desired in a wide range of applications such as nanobiosensing, nanoparticle based catalysis, and renewable energy generation using nanotechnology.

A review of heterogeneous photocatalysis for water and surface disinfection.

Photo-excitation of certain semiconductors can lead to the production of reactive oxygen species that can inactivate microorganisms. The mechanisms involved are reviewed, along with two important applications. The first is the use of photocatalysis to enhance the solar disinfection of water. It is estimated that 750 million people do not have accessed to an improved source for drinking and many more rely on sources that are not safe. If one can utilize photocatalysis to enhance the solar disinfection of water and provide an inexpensive, simple method of water disinfection, then it could help reduce the risk of waterborne disease. The second application is the use of photocatalytic coatings to combat healthcare associated infections. Two challenges are considered, i.e., the use of photocatalytic coatings to give "self-disinfecting" surfaces to reduce the risk of transmission of infection via environmental surfaces, and the use of photocatalytic coatings for the decontamination and disinfection of medical devices. In the final section, the development of novel photocatalytic materials for use in disinfection applications is reviewed, taking account of materials, developed for other photocatalytic applications, but which may be transferable for disinfection purposes.