Role of excited-state hydrogen bonding in CO2 photoreduction catalyzed by sodium magnesium chlorophyll.

In this paper, we report a joint experimental and computational study to elaborate the mechanism for the photocatalytic CO2 reduction reaction (CO2RR). Experimental results indicate that the catalyst (sodium magnesium chlorophyll, MgChlNa2), which has a well-defined structure for calculation and understanding, can achieve the photoreduction of CO2 to CO only using water as a dispersant, without adding any photosensitizer or sacrificial agent. Subsequently, a series of structural models of the hydrogen-bonded complexes of the catalyst were constructed and outlined via utilizing density functional theory (DFT) calculations, including photophysical and photochemical processes. The results confirm that the rate-limiting step of the whole CO2RR was the intersystem crossing process. The electron and proton transfers involved in photophysical and photochemical processes are induced by hydrogen bonds in the excited states. The combination of experiments and calculations will provide an important reference for the design of high-efficiency photocatalysts in the photocatalytic CO2RR.

Optimization Design and Mechanical Performances of Plant-Mix Hot Recycled Asphalt Using Response Surface Methodology.

This study aimed to explore the influence of material design parameters on the physical and mechanical properties of recycled asphalt. A Box-Behnken design was employed to determine the optimal preparation scheme for 17 groups of recycled asphalt. The effects of styreneic methyl copolymer (SMC) regenerant content, styrene-butadiene-styrene (SBS)-modified asphalt content, and shear temperature on the mechanical properties of recycled asphalt were analyzed using conventional and high/low-temperature rheological tests. The optimal processing parameters were determined by a response surface model based on multiple response indexes. The results revealed that the SBS-modified asphalt content had the most significant effect on the penetration of recycled asphalt. An increase in SMC regenerant content led to a gradual decrease in the rutting factor, while SBS-modified asphalt content had the opposite effect. The usage of SMC regenerant helped to reduce non-recoverable creep compliance by adjusting the proportion of viscoelastic-plastic components in recycled asphalt. Furthermore, the stiffness modulus results indicated that the addition of SMC regenerant improved the recovery performance of recycled asphalt at a low temperature. The recommended contents of SMC regenerant and SBS-modified asphalt are 7.88% and 150%, respectively, with a shear temperature of 157.7 °C.

A Novel Single-Atom Electrocatalyst Ti1 /rGO for Efficient Cathodic Reduction in Hybrid Photovoltaics.

Single-atom catalysts (SACs) are a frontier research topic in the catalysis community. Carbon materials decorated with atomically dispersed Ti are theoretically predicted with many attractive applications. However, such material has not been achieved so far. Herein, a Ti-based SAC, consisting of isolated Ti anchored by oxygen atoms on reduced graphene oxide (rGO) (termed as Ti1 /rGO), is successfully synthesized. The structure of Ti1 /rGO is characterized by high-angle annular dark-field scanning transmission electron microscopy and X-ray absorption fine structure spectroscopy, being determined to have a five coordinated local structure TiO5 . When serving as non-Pt cathode material in dye-sensitized solar cells (DSCs), Ti1 /rGO exhibits high electrocatalytic activity toward the tri-iodide reduction reaction. The power conversion efficiency of DSCs based on Ti1 /rGO is comparable to that using conventional Pt cathode. The unique structure of TiO5 moieties and the crucial role of atomically dispersed Ti in Ti1 /rGO are well understood by experiments and density functional theory calculations. This emerging material shows potential applications in energy conversion and storage devices.

Characterization of Asphalt Mixture Moduli under Different Stress States.

Modulus testing methods under various test conditions have a large influence on modulus test results, which hinders the accurate evaluation of the stiffness of asphalt mixtures. In order to decrease the uncertainty in the stiffness characteristics of asphalt mixtures under various stress states, the traditional unconfined compression test, direct tensile test, and the synchronous test method, based on the indirect tension and four-point bending tests, were carried out for different loading frequencies. Results showed that modulus test results were highly sensitive to the shape, size, and stress state of the specimen. Additionally, existing modulus characteristics did not reduce these differences. There is a certain correlation between the elastic modulus ratio and the frequency ratio for asphalt under multiple stress states. The modulus, under multiple stress states, was processed using min⁻max normalization. Then, the standardization model for tensile and compressive characteristics of asphalt under diverse stress states was established based on the sample preparation, modulus ratio variations, and loading frequency ratio. A method for deriving other moduli from one modulus was realized. It is difficult to evaluate the stiffness performance in diverse stress states for asphalt by only using conventional compressive and tensile tests. However, taking into account the effects of stress states and loading frequencies, standardized models can be used to reduce or even eliminate these effects. The model realizes the unification of different modulus test results, and provides a theoretical, methodological, and technical basis for objectively evaluating moduli.