Photocatalytic CO2 reduction with a quantum efficiency exceeding 60%: time-resolved spectroscopic and X-ray studies on Cu(I) photosensitizers in coordinative interaction with Co(II) phthalocyanine catalysts

The utilization of a fully noble-metal-free system for photocatalytic CO2 reduction remains a fundamental challenge, demanding the precise design of photosensitizers and catalysts, as well as the exploitation of their intermolecular interactions to facilitate electron delivery. Herein, we have implemented triple modulations on catalyst, photosensitizer and coordinative interaction between them for high-performance light-driven CO2 reduction. In this study, heteroleptic copper and cobalt phthalocyanine complexes were selected as photosensitizers and catalysts, respectively. An over ten-fold improvement in light-driven reduction of CO2 to CO is achieved for the catalysts with appending electron-withdrawing substituents for optimal CO-desorption ability. In addition, pyridine substituents were implanted at the backbone of the phenanthroline moiety of the Cu(I) photosensitizers and the effect of their axial coordinative interaction with the catalyst was tested. The combined results of 1H NMR titration experiment, steady-state/transient photoluminescence, and transient absorption spectroscopy confirm the coordinative interaction and reductive quenching pathway in photocatalysis corroboratively. It has been found that the catalytic performances of the coordinatively interacted systems are unexpectedly reverse to those with the pyridine-free Cu(I) photosensitizers. Moreover, the latter system enables a very high quantum efficiency up to 63.5% at 425 nm with a high selectivity exceeding 99% for CO2-to-CO conversion. As determined by time-resolved X-ray absorption spectroscopy and DFT calculation, the replacement of phenyl by pyridyl groups in the Cu(I) photosensitizer favors a stronger flattening and larger torsional angle change of the overall excited state geometry upon photoexcitation, which explains the decreased lifetime of the triplet excited state. Our work promotes the systematic multi-pathway optimizations on the catalyst, photosensitizer and their interactions for advanced CO2 photoreduction.

Electroplating Deposition of Bismuth Absorbers for X-ray Superconducting Transition Edge Sensors

An absorber with a high absorbing efficiency is crucial for X-ray transition edge sensors (TESs) to realize high quantum efficiency and the best energy resolution. Semimetal Bismuth (Bi) has shown greater superiority than gold (Au) as the absorber due to the low specific heat capacity, which is two orders of magnitude smaller. The electroplating process of Bi films is investigated. The Bi grains show a polycrystalline rhombohedral structure, and the X-ray diffraction (XRD) patterns show a typical crystal orientation of (012). The average grain size becomes larger as the electroplating current density and the thickness increase, and the orientation of Bi grains changes as the temperature increases. The residual resistance ratio (RRR) (R300 K/R4.2 K) is 1.37 for the Bi film (862 nm) deposited with 9 mA/cm2 at 40 °C for 2 min. The absorptivity of the 5 μm thick Bi films is 40.3% and 30.7% for 10 keV and 15.6 keV X-ray radiation respectively, which shows that Bi films are a good candidate as the absorber of X-ray TESs.

High Performance Predictable Quantum Efficient Detector Based on Induced-Junction Photodiodes Passivated with SiO2/SiNx

We performed a systematic study involving simulation and experimental techniques to develop induced-junction silicon photodetectors passivated with thermally grown SiO2 and plasma-enhanced chemical vapor deposited (PECVD) SiNx thin films that show a record high quantum efficiency. We investigated PECVD SiNx passivation and optimized the film deposition conditions to minimize the recombination losses at the silicon–dielectric interface as well as optical losses. Depositions with varied process parameters were carried out on test samples, followed by measurements of minority carrier lifetime, fixed charge density, and optical absorbance and reflectance. Subsequently, the surface recombination velocity, which is the limiting factor for internal quantum deficiency (IQD), was obtained for different film depositions via 2D simulations where the measured effective lifetime, fixed charge density, and substrate parameters were used as input. The quantum deficiency of induced-junction photodiodes that would be fabricated with a surface passivation of given characteristics was then estimated using improved 3D simulation models. A batch of induced-junction photodiodes was fabricated based on the passivation optimizations performed on test samples and predictions of simulations. Photodiodes passivated with PECVD SiNx film as well as with a stack of thermally grown SiO2 and PECVD SiNx films were fabricated. The photodiodes were assembled as light-trap detector with 7-reflections and their efficiency was tested with respect to a reference Predictable Quantum Efficient Detector (PQED) of known external quantum deficiency. The preliminary measurement results show that PQEDs based on our improved photodiodes passivated with stack of SiO2/SiNx have negligible quantum deficiencies with IQDs down to 1 ppm within 30 ppm measurement uncertainty.

Kinetics and Energetics of Intramolecular Electron Transfer in Single-Point Labeled TUPS-Cytochrome c Derivatives

Electron transfer within and between proteins is a fundamental biological phenomenon, in which efficiency depends on several physical parameters. We have engineered a number of horse heart cytochrome c single-point mutants with cysteine substitutions at various positions of the protein surface. To these cysteines, as well as to several native lysine side chains, the photoinduced redox label 8-thiouredopyrene-1,3,6-trisulfonate (TUPS) was covalently attached. The long-lived, low potential triplet excited state of TUPS, generated with high quantum efficiency, serves as an electron donor to the oxidized heme c. The rates of the forward (from the label to the heme) and the reverse (from the reduced heme back to the oxidized label) electron transfer reactions were obtained from multichannel and single wavelength flash photolysis absorption kinetic experiments. The electronic coupling term and the reorganization energy for electron transfer in this system were estimated from temperature-dependent experiments and compared with calculated parameters using the crystal and the solution NMR structure of the protein. These results together with the observation of multiexponential kinetics strongly support earlier conclusions that the flexible arm connecting TUPS to the protein allows several shortcut routes for the electron involving through space jumps between the label and the protein surface.

Preparation and Characterization of Tubelike g-C3N4/Ag3PO4 Heterojunction with Enhanced Visible-Light Photocatalytic Activity

Water pollution caused by dye wastewater is a potential threat to human health. Using photocatalysis technology to deal with dye wastewater has the advantages of strong purification and no secondary pollution, so it is greatly significant to look for new visible-light photocatalysts with high photocatalytic ability for dye wastewater degradation. Semiconductor photocatalyst silver phosphate (Ag3PO4) has high quantum efficiency and photocatalytic degradation activity. However, Ag3PO4 is prone to photoelectron corrosion and becomes unstable during photocatalysis, which severely limits its application in this field. In this study, a tubelike g-C3N4/Ag3PO4 heterojunction was constructed by the chemical precipitation method. An Ag3PO4 nanoparticle was loaded onto the surface of the tubelike g-C3N4, forming close contact. The photocatalytic activity of the photocatalyst was evaluated by the degradation of RhB under visible-light irradiation. The tubelike g-C3N4/Ag3PO4-5% heterojunction exhibited optimal photocatalytic performance. In an optimal process, the degradation rate of the RhB is 90% under visible-light irradiation for 40 min. The recycling experiment showed that there was no apparent decrease in the activity of tubelike g-C3N4/Ag3PO4-5% heterojunction after five consecutive runs. A possible Z-type mechanism is proposed to explain the high activity and stability of the heterojunction.