Enhanced Visible Light-Driven Photocatalytic Water-Splitting Reaction of Titanate Nanotubes Sensitised with Ru(II) Bipyridyl Complex.

The ion exchange of Na+ cations was used to photosensitise titanates nanotubes (Ti-NTs) with tris(2,2'-bipyridine)ruthenium(II) cations (Ru(bpy)32+); this yielded a light-sensitised Ti-NTs composite denoted as (Ru(bpy)3)Ti-NTs, exhibiting the characteristic absorption of Ru(bpy)32+ in visible light. Incident photon-to-current efficiency (IPCE) measurements and the photocatalytic reduction of methyl viologen reaction confirmed that in the photosensitisation of the (Ru(bpy)3)Ti-NTs composite, charge transfer and charge separation occur upon excitation by ultraviolet and visible light irradiation. The photocatalytic potential of titanate nanotubes was tested in the water-splitting reaction and the H2 evolution reaction using a sacrificial agent and showed photocatalytic activity under various light sources, including xenon-mercury lamp, simulated sunlight, and visible light. Notably, in the conditions of the H2 evolution reaction when (Ru(bpy)3)Ti-NTs were submitted to simulated sunlight, they exceeded the photocatalytic activity of pristine Ti-NTs and TiO2 by a factor of 3 and 3.5 times, respectively. Also, (Ru(bpy)3)Ti-NTs achieved the photocatalytic water-splitting reaction under simulated sunlight and visible light, producing, after 4 h, 199 and 282 µmol×H2×gcat-1. These results confirm the effective electron transfer of Ru(bpy)3 to titanate nanotubes. The stability of the photocatalyst was evaluated by a reuse test of four cycles of 24 h reactions without considerable loss of catalytic activity and crystallinity.

Multi-element analysis of tyre rubber for metal tracers.

The purpose of this study was to identify a characteristic elemental tyre fingerprint that can be utilised in atmospheric source apportionment calculations. Currently zinc is widely used as a single element tracer to quantify tyre wear, however several authors have highlighted issues with this approach. To overcome this, tyre rubber tread was digested and has been analysed for 25 elements by ICP-MS to generate a multielement profile. Additionally, to estimate the percentage of the tyre made up of inert fillers, thermogravimetric analysis was performed on a subset. Comparisons were made between passenger car and heavy goods vehicle tyre composition, and a subset of tyres had both tread and sidewall sampled for further comparison. 19 of the 25 elements were detected in the analysis. The mean mass fraction of zinc detected was 11.17 g/kg, consistent with previous estimates of 1% of the tyre mass. Aluminium, iron, and magnesium were found to be the next most abundant elements. Only one source profile for tyre wear exists in both the US and EU air pollution species profile databases, highlighting the need for more recent data with better coverage of tyre makes and models. This study provides data on new tyres which are currently operating on-road in Europe and is therefore relevant for ongoing atmospheric studies assessing the levels of tyre wear particles in urban areas.

Towards Portable MEMS Oscillators for Sensing Nanoparticles.

This paper reports on the design, and implementation of piezoelectric-on-silicon MEMS resonators installed within a portable experimental setup for sensing nanoparticles in a laboratory environment. MEMS oscillators with a center frequency of approximately 5.999 MHz are employed for sensing 50 nm size-selected silver nanoparticles generated in the laboratory. The same experimental setup is then assembled to sense indoor particles that are present in the laboratory environment. The challenges associated with particle deposition as a result of assembling the portable experimental setup is highlighted. Furthermore, the MEMS oscillators demonstrate that the total mass of silver nanoparticles deposited onto the MEMS resonator surface using the inertial impaction technique-based experimental setup is approximately 7.993 nanograms. The total indoor particle mass accumulated on the MEMS resonator surface is estimated to be approximately 1.732 nanograms and 26.9 picograms for two different runs. The frequency resolution of the MEMS oscillator is estimated to be approximately 32 ppb and, consequently, the minimum detectable particle mass is approximately 60 femtograms for a 9.2 s integration time.

Source terms for benchmarking models of SARS-CoV-2 transmission via aerosols and droplets.

There is ongoing and rapid advancement in approaches to modelling the fate of exhaled particles in different environments relevant to disease transmission. It is important that models are verified by comparison with each other using a common set of input parameters to ensure that model differences can be interpreted in terms of model physics rather than unspecified differences in model input parameters. In this paper, we define parameters necessary for such benchmarking of models of airborne particles exhaled by humans and transported in the environment during breathing and speaking.

Utah Wintertime Measurements of Heavy-Duty Vehicle Nitrogen Oxide Emission Factors.

There have only been a few wintertime studies of heavy-duty vehicle (HDV) NOx emissions in the United States, and while they have observed increased emissions, fleet characterization to identify the cause has been lacking. We have collected wintertime measurements of NOx emission factors from 1591 HDVs at a Utah Port of Entry in December 2020 that includes individual vehicle identification. In general, NOx emission factors for 2011 and newer chassis model year HDV are significantly higher than those for 2017 spring measurements from California. The newest chassis model year HDV (2017-2021) NOx emission factors are similar, indicating no significant emission deterioration over the 5 year period, though they are still approximately a factor of 3 higher than the portable emission measurement on-road enforcement standard. We estimate that ambient temperature increases NOx emissions no more than 25% in the newer HDV, likely through reductions in catalyst efficiencies. NOx emissions increase to a significantly higher level for the 2011-2013 chassis model year vehicles, where within the uncertainties, they have emissions similar to older precontrol vehicles, indicating that they have lost their NOx control capabilities within 8 years. MOVES3 modeling of the Utah fleet underpredicted mean NOx emissions by a factor of 1.8 but the MOVES3 estimate is helped by including a larger fraction of high-emitting glider kit trucks (new chassis with pre-emission control engines) than found in the observations.

Weakly Coupled Piezoelectric MEMS Resonators for Aerosol Sensing.

This paper successfully demonstrates the potential of weakly coupled piezoelectric MEMS (Micro-Electro-Mechanical Systems) gravimetric sensors for the detection of ultra-fine particulates. As a proof-of-principle, the detection of diesel soot particles of 100 nanometres or less is demonstrated. A practical monitoring context also exists for diesel soot particles originating from combustion engines, as they are of serious health concern. The MEMS sensors employed in this work operate on the principle of vibration mode-localisation employing an amplitude ratio shift output metric for readout. Notably, gains are observed while comparing parametric sensitivities and the input referred stability for amplitude ratio and resonant frequency variations, demonstrating that the amplitude ratio output metric is particularly suitable for long-term measurements. The soot particle mass directly estimated using coupled MEMS resonators can be correlated to the mass, indirectly estimated using the condensation particle counter used as the reference instrument.

Comprehensive characterization of mainstream marijuana and tobacco smoke.

Recent increases in marijuana use and legalization without adequate knowledge of the risks necessitate the characterization of the billions of nanoparticles contained in each puff of smoke. Tobacco smoke offers a benchmark given that it has been extensively studied. Tobacco and marijuana smoke particles are quantitatively similar in volatility, shape, density and number concentration, albeit with differences in size, total mass and chemical composition. Particles from marijuana smoke are on average 29% larger in mobility diameter than particles from tobacco smoke and contain 3.4× more total mass. New measurements of semi-volatile fractions determine over 97% of the mass and volume of the particles from either smoke source are comprised of semi-volatile compounds. For tobacco and marijuana smoke, respectively, 4350 and 2575 different compounds are detected, of which, 670 and 536 (231 in common) are tentatively identified, and of these, 173 and 110 different compounds (69 in common) are known to cause negative health effects through carcinogenic, mutagenic, teratogenic, or other toxic mechanisms. This study demonstrates striking similarities between marijuana and tobacco smoke in terms of their physical and chemical properties.

A Simple Method for Measuring Fine-to-Ultrafine Aerosols Using Bipolar Charge Equilibrium.

Low-cost methods for measuring airborne microparticles and nanoparticles (aerosols) have remained elusive despite the increasing concern of health impacts from ambient, urban, and indoor sources. While bipolar ion sources are common in smoke alarms, this work is the first to exploit the mean charge on an aerosol resulting from a bipolar charge equilibrium and establish experimentally its correlation to properties of the aerosol particle size distribution. The net current produced from this mean particle charge is demonstrated to be linearly proportional to the product of the mean particle diameter and total number concentration (i ∼ Nd̅) for two bipolar ion sources (85Kr and 241Am). This conclusion is supported by simple equations derived from well-established bipolar charging theory. The theory predicts that the mean charge on the aerosol particles reaches an equilibrium, which, importantly, is independent of the concentration of charging ions. Furthermore, in situ measurements of a roadside aerosol demonstrate that the sensing method yields results in good agreement (R2 = 0.979) with existing portable and laboratory-grade aerosol instruments. The simplicity, stability, and cost of the bipolar ion source overcome challenges of other portable sensors, increasing the feasibility of widespread sensor deployment to monitor ultrafine particle characteristics, which are relevant to lung deposition and by extension, human health.

Continuous-Flow Synthesis of Carbon-Coated Silicon/Iron Silicide Secondary Particles for Li-Ion Batteries.

The development of better Li-ion battery (LIB) electrodes requires an orchestrated effort to improve the active materials as well as the electron and ion transport in the electrode. In this paper, iron silicide is studied as an anode material for LIBs because of its higher conductivity and lower volume expansion compared to pure Si particles. In addition, carbon nanotubes (CNTs) can be synthesized from the surface of iron-silicides using a continuous flow coating process where precursors are first spray dried into micrometer-scale secondary particles and are then flown through a chemical vapor deposition (CVD) reactor. Some CNTs are formed inside the secondary particles, which are important for short-range electrical transport and good utilization of the active material. Surface-bound CNTs on the secondary particles may help establish a long-range conductivity. We also observed that these spherical secondary particles allow for better electrode coating quality, cyclability, and rate performance than unstructured materials with the same composition. The developed electrodes retain a gravimetric capacity of 1150 mAh/g over 300 cycles at 1A/g as well as a 43% capacity retention at a rate of 5 C. Further, blended electrodes with graphite delivered a 539 mAh/g with high electrode density (∼1.6 g/cm3) and areal capacity (∼3.5 mAh/cm2) with stable cycling performance.

Agglomeration Dynamics of 1D Materials: Gas-Phase Collision Rates of Nanotubes and Nanorods.

The agglomeration and self-assembly of gas-phase 1D materials in anthropogenic and natural systems dictate their resulting nanoscale morphology, multiscale hierarchy, and ultimate macroscale properties. Brownian motion induces collisions, upon which 1D materials often restructure to form bundles and can lead to aerogels. Herein, the first results of collision rates for 1D nanomaterials undergoing thermal transport are presented. The Langevin dynamic simulations of nanotube rotation and translation demonstrate that the collision kernels for rigid nanotubes or nanorods are ≈10 times greater than spherical systems. Resulting reduced order equations allow straightforward calculation of the physical parameters to determine the collision kernel for straight and curved 1D materials from 102 to 106 nm length. The collision kernels of curved 1D structures increase ≈1.3 times for long (>102 nm), and ≈5 times for short (≈102 nm) relative to rigid materials. Applications of collision frequencies allow the first kinetic analysis of aerogel self-assembly from gas-phase carbon nanotubes (CNTs). The timescales for CNT collision and bundle formation (0.3-42 s) agree with empirical residence times in CNT reactors (3-15 s). These results provide insights into the CNT length, number, and timescales required for aerogel formation, which bolsters our understanding of mass-produced 1D aerogel materials.

The Dependence of CNT Aerogel Synthesis on Sulfur-driven Catalyst Nucleation Processes and a Critical Catalyst Particle Mass Concentration.

The floating catalyst chemical vapor deposition (FC-CVD) process permits macro-scale assembly of nanoscale materials, enabling continuous production of carbon nanotube (CNT) aerogels. Despite the intensive research in the field, fundamental uncertainties remain regarding how catalyst particle dynamics within the system influence the CNT aerogel formation, thus limiting effective scale-up. While aerogel formation in FC-CVD reactors requires a catalyst (typically iron, Fe) and a promotor (typically sulfur, S), their synergistic roles are not fully understood. This paper presents a paradigm shift in the understanding of the role of S in the process with new experimental studies identifying that S lowers the nucleation barrier of the catalyst nanoparticles. Furthermore, CNT aerogel formation requires a critical threshold of FexCy > 160 mg/m3, but is surprisingly independent of the initial catalyst diameter or number concentration. The robustness of the critical catalyst mass concentration principle is proved further by producing CNTs using alternative catalyst systems; Fe nanoparticles from a plasma spark generator and cobaltocene and nickelocene precursors. This finding provides evidence that low-cost and high throughput CNT aerogel routes may be achieved by decoupled and enhanced catalyst production and control, opening up new possibilities for large-scale CNT synthesis.

How Well Do We Know the Future of CO2 Emissions? Projecting Fleet Emissions from Light Duty Vehicle Technology Drivers.

While the UK has committed to reduce CO2 emissions to 80% of 1990 levels by 2050, transport accounts for nearly a fourth of all emissions and the degree to which decarbonization can occur is highly uncertain. We present a new methodology using vehicle and powertrain parameters within a Bayesian framework to determine the impact of engineering vehicle improvements on fuel consumption and CO2 emissions. Our results show how design changes in vehicle parameters (e.g., mass, engine size, and compression ratio) result in fuel consumption improvements from a fleet-wide mean of 5.6 L/100 km in 2014 to 3.0 L/100 km by 2030. The change in vehicle efficiency coupled with increases in vehicle numbers and fleet-wide activity result in a total fleet-wide reduction of 41 ± 10% in 2030, relative to 2012. Concerted internal combustion engine improvements result in a 48 ± 10% reduction of CO2 emissions, while efforts to increase the number of diesel vehicles within the fleet had little additional effect. Increasing plug-in and all-electric vehicles reduced CO2 emissions by less (42 ± 10% reduction) than concerted internal combustion engines improvements. However, if the grid decarbonizes, electric vehicles reduce emissions by 45 ± 9% with further reduction potential to 2050.

Greenhouse Gas and Noxious Emissions from Dual Fuel Diesel and Natural Gas Heavy Goods Vehicles.

Dual fuel diesel and natural gas heavy goods vehicles (HGVs) operate on a combination of the two fuels simultaneously. By substituting diesel for natural gas, vehicle operators can benefit from reduced fuel costs and as natural gas has a lower CO2 intensity compared to diesel, dual fuel HGVs have the potential to reduce greenhouse gas (GHG) emissions from the freight sector. In this study, energy consumption, greenhouse gas and noxious emissions for five after-market dual fuel configurations of two vehicle platforms are compared relative to their diesel-only baseline values over transient and steady state testing. Over a transient cycle, CO2 emissions are reduced by up to 9%; however, methane (CH4) emissions due to incomplete combustion lead to CO2e emissions that are 50-127% higher than the equivalent diesel vehicle. Oxidation catalysts evaluated on the vehicles at steady state reduced CH4 emissions by at most 15% at exhaust gas temperatures representative of transient conditions. This study highlights that control of CH4 emissions and improved control of in-cylinder CH4 combustion are required to reduce total GHG emissions of dual fuel HGVs relative to diesel vehicles.

Air quality and climate impacts of alternative bus technologies in Greater London.

The environmental impact of diesel-fueled buses can potentially be reduced by the adoption of alternative propulsion technologies such as lean-burn compressed natural gas (LB-CNG) or hybrid electric buses (HEB), and emissions control strategies such as a continuously regenerating trap (CRT), exhaust gas recirculation (EGR), or selective catalytic reduction with trap (SCRT). This study assessed the environmental costs and benefits of these bus technologies in Greater London relative to the existing fleet and characterized emissions changes due to alternative technologies. We found a >30% increase in CO2 equivalent (CO2e) emissions for CNG buses, a <5% change for exhaust treatment scenarios, and a 13% (90% confidence interval 3.8-20.9%) reduction for HEB relative to baseline CO2e emissions. A multiscale regional chemistry-transport model quantified the impact of alternative bus technologies on air quality, which was then related to premature mortality risk. We found the largest decrease in population exposure (about 83%) to particulate matter (PM2.5) occurred with LB-CNG buses. Monetized environmental and investment costs relative to the baseline gave estimated net present cost of LB-CNG or HEB conversion to be $187 million ($73 million to $301 million) or $36 million ($-25 million to $102 million), respectively, while EGR or SCRT estimated net present costs were $19 million ($7 million to $32 million) or $15 million ($8 million to $23 million), respectively.

Global civil aviation black carbon emissions.

Aircraft black carbon (BC) emissions contribute to climate forcing, but few estimates of BC emitted by aircraft at cruise exist. For the majority of aircraft engines the only BC-related measurement available is smoke number (SN)-a filter based optical method designed to measure near-ground plume visibility, not mass. While the first order approximation (FOA3) technique has been developed to estimate BC mass emissions normalized by fuel burn [EI(BC)] from SN, it is shown that it underestimates EI(BC) by >90% in 35% of directly measured cases (R(2) = -0.10). As there are no plans to measure BC emissions from all existing certified engines-which will be in service for several decades-it is necessary to estimate EI(BC) for existing aircraft on the ground and at cruise. An alternative method, called FOX, that is independent of the SN is developed to estimate BC emissions. Estimates of EI(BC) at ground level are significantly improved (R(2) = 0.68), whereas estimates at cruise are within 30% of measurements. Implementing this approach for global civil aviation estimated aircraft BC emissions are revised upward by a factor of ~3. Direct radiative forcing (RF) due to aviation BC emissions is estimated to be ~9.5 mW/m(2), equivalent to ~1/3 of the current RF due to aviation CO2 emissions.

Effects of ethanol on vehicle energy efficiency and implications on ethanol life-cycle greenhouse gas analysis.

Bioethanol is the world's largest-produced alternative to petroleum-derived transportation fuels due to its compatibility within existing spark-ignition engines and its relatively mature production technology. Despite its success, questions remain over the greenhouse gas (GHG) implications of fuel ethanol use with many studies showing significant impacts of differences in land use, feedstock, and refinery operation. While most efforts to quantify life-cycle GHG impacts have focused on the production stage, a few recent studies have acknowledged the effect of ethanol on engine performance and incorporated these effects into the fuel life cycle. These studies have broadly asserted that vehicle efficiency increases with ethanol use to justify reducing the GHG impact of ethanol. These results seem to conflict with the general notion that ethanol decreases the fuel efficiency (or increases the fuel consumption) of vehicles due to the lower volumetric energy content of ethanol when compared to gasoline. Here we argue that due to the increased emphasis on alternative fuels with drastically differing energy densities, vehicle efficiency should be evaluated based on energy rather than volume. When done so, we show that efficiency of existing vehicles can be affected by ethanol content, but these impacts can serve to have both positive and negative effects and are highly uncertain (ranging from -15% to +24%). As a result, uncertainties in the net GHG effect of ethanol, particularly when used in a low-level blend with gasoline, are considerably larger than previously estimated (standard deviations increase by >10% and >200% when used in high and low blends, respectively). Technical options exist to improve vehicle efficiency through smarter use of ethanol though changes to the vehicle fleets and fuel infrastructure would be required. Future biofuel policies should promote synergies between the vehicle and fuel industries in order to maximize the society-wise benefits or minimize the risks of adverse impacts of ethanol.

Gas-phase production of gold-decorated silica nanoparticles.

Gold-decorated silica nanoparticles were synthesized in a two-step process in which silica nanoparticles were produced by chemical vapor synthesis using tetraethylorthosilicate (TEOS) and subsequently decorated using two different gas-phase evaporative techniques. Both evaporative processes resulted in gold decoration of the silica particles. This study compares the mechanisms of particle decoration for a production method in which the gas and particles remain cool to a method in which the entire aerosol is heated. Results of transmission electron microscopy and visible spectroscopy studies indicate that both methods produce particles with similar morphologies and nearly identical absorption spectra, with peak absorption at 500-550 nm. A study of the thermal stability of the particles using heated-TEM indicates that the gold decoration on the particle surface remains stable at temperatures below 900 °C, above which the gold decoration begins to both evaporate and coalesce.

SiO2 coating of silver nanoparticles by photoinduced chemical vapor deposition.

Gas-phase silver nanoparticles were coated with silicon dioxide (SiO2) by photoinduced chemical vapor deposition (photo-CVD). Silver nanoparticles, produced by inert gas condensation, and a SiO2 precursor, tetraethylorthosilicate (TEOS), were exposed to vacuum ultraviolet (VUV) radiation at atmospheric pressure and varying temperatures. The VUV photons dissociate the TEOS precursor, initiating a chemical reaction that forms SiO2 coatings on the particle surfaces. Coating thicknesses were measured for a variety of operation parameters using tandem differential mobility analysis and transmission electron microscopy. The chemical composition of the particle coatings was analyzed using energy dispersive x-ray spectrometry and Fourier transform infrared spectroscopy. The highest purity films were produced at 300-400 degrees C with low flow rates of additional oxygen. The photo-CVD coating technique was shown to effectively coat nanoparticles and limit core particle agglomeration at concentrations up to 10(7) particles cm(-3).