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.

Ce:LaB3O6 glass for high-resolution radiation dosimetry

Ce:LaB3O6 (LBO) glass, whose constituents are abundant elements and fabrication is easy and cheap, is found to be a promising thermoluminescence (TL) dosimeter. This is originally achieved by CeF3 doping and melting under a reducing atmosphere, with the optimum concentration of 0.1% (quantum efficiency = 66%). The corresponding Ce interatomic distance is ~ 4 nm, below which concentration quenching occurs via Ce dipole-dipole interaction, as elucidated experimentally by Dexter’s theory. Ce:LBO exhibits a good dose resolution, with a linear dependence covering five orders of magnitude on both irradiation-dose and TL-response. Furthermore, it can be cyclically irradiated and read without degradation.

Generalization of Kirchhoff’s Law: The inherent relations between quantum efficiency and emissivity

Planck’s law of thermal radiation depends on the temperature, \(T\), and the emissivity, \(\epsilon\), which is the coupling of heat to radiation depending on both phonon-electron nonradiative-interactions and electron-photon radiative-interactions. In contrast, absorptivity, \(\alpha\), only depends on the electron-photon radiative-interactions. At thermodynamic equilibrium, nonradiative-interactions are balanced, resulting in Kirchhoff’s law of thermal radiation, \(\epsilon =\alpha\). For non-equilibrium, Quantum efficiency (QE) describes the statistics of photon emission, which like emissivity depends on both radiative and nonradiative interactions. Past generalized Planck’s equation extends Kirchhoff’s law out of equilibrium by scaling the emissivity with the pump-dependent chemical-potential \(\mu\), obscuring the relations between the body properties. Here we theoretically and experimentally demonstrate a prime equation relating these properties in the form of \(\epsilon =\alpha \left(1-QE\right)\). At equilibrium, these relations are reduced to Kirchhoff’s law. Our work lays out the evolution of non-thermal emission with temperature, which is critical for the development of lighting and energy devices.

Single-atom Cu anchored catalysts for photocatalytic renewable H2 production with a quantum efficiency of 56%

Single-atom catalysts anchoring offers a desirable pathway for efficiency maximization and cost-saving for photocatalytic hydrogen evolution. However, the single-atoms loading amount is always within 0.5% in most of the reported due to the agglomeration at higher loading concentrations. In this work, the highly dispersed and large loading amount (>1 wt%) of copper single-atoms were achieved on TiO2, exhibiting the H2 evolution rate of 101.7 mmol g−1 h−1 under simulated solar light irradiation, which is higher than other photocatalysts reported, in addition to the excellent stability as proved after storing 380 days. More importantly, it exhibits an apparent quantum efficiency of 56% at 365 nm, a significant breakthrough in this field. The highly dispersed and large amount of Cu single-atoms incorporation on TiO2 enables the efficient electron transfer via Cu2+-Cu+ process. The present approach paves the way to design advanced materials for remarkable photocatalytic activity and durability.

Air-processed stable near-infrared Si-based perovskite light-emitting devices with efficiency exceeding 7.5%

Two composite layers are used to enhance the efficiency of Si-based near-infrared perovskite light-emitting devices, which are produced in ambient air, and the external quantum efficiency increased to 7.5%.