Tuning Structures and Microenvironments of Cu-Based Catalysts for Sustainable CO₂ and CO Electroreduction

ConspectusThe carbon balance has been disrupted by the widespread use of fossil fuels and subsequent excessive emissions of carbon dioxide (CO2), which has become an increasingly critical environmental challenge for human society. The production and use of renewable energy sources and/or chemicals have been proposed as important strategies to reduce emissions, of which the electrochemical CO2 (or CO) reduction reaction (CO2RR/CORR) in the aqueous systems represents a promising approach.Benefitted by the capacity of manufacturing high-value-added products (e.g., ethylene, ethanol, formic acid, etc.) with a net-zero carbon emission, copper-based CO2RR/CORR powered by sustainable electricity is regarded as a potential candidate for carbon neutrality. However, the diversity of selectivities in copper-based systems poses a great challenge to the research in this field and sets a great obstacle for future industrialization.To date, scientists have revealed that the electrocatalyst design and preparation play a significant role in achieving efficient and selective CO2-to-chemical (or CO-to-chemical) conversion. Although substantial efforts have been dedicated to the catalyst preparation and corresponding electrosynthesis of sustainable chemicals from CO2/CO so far, most of them are still derived from empirical or random searches, which are relatively inefficient and cost-intensive. Most of the mechanism studies have suggested that both intrinsic properties (such as electron states) and extrinsic environmental factors (such as surface energy) of a catalyst can significantly alter catalytic performance. Thus, these two topics are mainly discussed for copper-based catalyst developments in this Account.Here, we provided a concise and comprehensive introduction to the well-established strategies employed for the design of copper-based electrocatalysts for CO2RR/CORR. We used several examples from our research group, as well as representative studies of other research groups in this field during the recent five years, with the perspectives of tuning local electron states, regulating alloy phases, modifying interfacial coverages, and adjusting other interfacial microenvironments (e.g., molecule modification or surface energy). Finally, we employed the techno-economic assessment with a viewpoint on the future application of CO2/CO electroreduction in manufacturing sustainable chemicals. Our study indicates that when carbon price is taken into account, the electrocatalytic CO2-to-chemical conversion can be more market-competitive, and several potential value-added products including formate, methanol, ethylene, and ethanol can all make profits under optimal operating conditions. Moreover, a downstream module employing traditional chemical industrial processes (e.g., thermal polymerization, catalytic hydrolysis, or condensation process) will also make the whole electrolysis system profitable in the future. These design principles, combined with the recent advances in the development of efficient copper-based electrocatalysts, may provide a low-cost and long-lasting catalytic system for a profitable industrial-scale CO2RR in the future

Two-Photon Pumped Amplified Spontaneous Emission and Lasing from Formamidinium Lead Bromine Nanocrystals

Formamidinium (FA) perovskites have exhibited outstanding optoelectronic properties in solar cells and light-emitting diodes. However, their development on nanolaser application have rarely been explored, especially the up-conversion lasing performance. Here, the two-photon pumped lasing from colloidal FA-perovskite nanocrystals (NCs) is realized at room temperature, which are prepared by a ligand-assisted reprecipitation strategy. These colloidal FAPbX3 NCs exhibit high-quality cubic phase and tunable bright emission (from 433 to 667 nm). By tuning the ratio of the surface organic ligands, the morphology of FAPbBr3 NCs can be transferred from quantum dots to nanoplatelets, consequently the emission can be tuned in 520–542 nm. In addition, the low-threshold amplified spontaneous emission (ASE) under both two- and one-photon excitations is demonstrated benefiting from the large two-photon absorption coefficient (0.76 cm/GW) and high optical net gain (480 cm–1), indicating that FAPbX3 NCs can be regarded as an excellent optical gain medium. The strong temperature-tolerent ASE action with a high characteristic temperature of 308 K indicates the weak requirements of heat management of FA-based devices. Finally, as we couple FAPbBr3 into a hollow capillary tube, stable two-photon excited whispering-gallery-mode lasing is successfully achieved with a low threshold of ∼310 μJ/cm2. Our findings suggest that FAPbX3 NCs can act as excellent gain media for high-performance upconverted nanolasers toward optoelectronic application

Low Threshold and Ultrastability of One-Step Air-Processed All-Inorganic CsPbX₃ Thin Films toward Full-Color Visible Amplified Spontaneous Emission

All-inorganic perovskites (CsPbX3) with the merits of high stability and remarkable optical gain property are attractive for achieving on-chip coherent light sources. Unfortunately, traditional solution-processed CsPbX3 films suffer from inevitable poor surface integrity and pinhole defects, severely hindering their optical properties. Here, from the perspective of precursor solution chemistry, we use an ionic liquid solvent methylammonium acetate (MAAc) to fabricate compact, pinhole-free, and smooth CsPbX3 thin films in a one-step air process without antisolvent treatment. Optically pumped amplified spontaneous emission (ASE) with a straightforward visible spectral tunability (418–725 nm) is achieved under both nanosecond and femtosecond laser excitation. For the representative CsPbBr3 films, the threshold reaches down to 11.4 μJ cm–2 under nanosecond laser pumping, which is comparable to the value under one-photon femtosecond pumping. The long gain lifetime up to 258.2 ps is revealed by transient absorption spectroscopy. Most importantly, the films show excellent optical stability and humidity stability with no obvious degradation under the pulsed laser irradiation for more than 210 min, stable ASE output under 95% high humidity, and conspicuous ASE after 1000 h of storage in air condition without encapsulation. These results demonstrate that the method of fabricating inorganic perovskite films with an ionic liquid solvent is promising in developing high-performance full-color visible lasers

Hot Carrier Transfer in PtSe₂/Graphene Enabled by the Hot Phonon Bottleneck

The charge transfer (CT) process of two-dimensional (2D) graphene/transition metal dichalcogenides (TMDs) heterostructures makes the photoelectric conversion ability of TMDs into a wider spectral range for the light harvester and photoelectric detector applications. However, the direct in situ investigation of the hot carrier transport in graphene/TMDs heterostructures has been rarely reported. Herein, using the optical pump and a terahertz (THz) probe (OPTP) spectroscopy, the CT process from graphene to five-layer PtSe2 in the PtSe2/graphene (P/G) heterostructure is demonstrated to be related to the pump fluence, which is enabled by the hot phonon bottleneck (HPB) effect in graphene. Furthermore, the frequency dispersion conductivity and the THz emission spectroscopy of the P/G heterostructure confirmed the existence of interlayer CT and its pump fluence-dependent behavior. Our results provide in-depth physical insights into the CT mechanism at the P/G van der Waals interface, which is crucial for further exploration of optoelectronic devices based on P/G heterostructures

Ionic Solvent-Assisted MAPbBr₃ Perovskite Film for Two-Photon Pumped Single-Mode Laser

Miniaturized coherent light sources on the nanoscale are highly desired for on-chip photonics integration. However, when approaching the diffraction limit, the sub-wavelength-scale all-dielectric lasers are difficult to realize due to the trade-off between lasing performance and physical size. Especially for a thin-film laser, usually an externally complex cavity is required to provide the necessary optical feedback. Herein, we successfully shrink the MAPbBr3 perovskite thin-film laser to sub-wavelength scale (300 nm) with simplified cavity design using only an ultraviolet glue layer and a quartz glass. The morphology quality and the gain properties of the film are enhanced by introducing ionic liquid. Consequently, the stable and low-threshold single-mode laser with a highly linear polarization degree of 78.6% and a narrow line width of 0.35 nm is achieved under two-photon excitation. The excellent single-mode laser with sub-wavelength scale and ultrasimplified structure could provide a facile and versatile platform for future integrated optoelectronic devices

Robust Subwavelength Single-Mode Perovskite Nanocuboid Laser

On-chip photonic information processing systems require great research efforts toward miniaturization of the optical components. However, when approaching the classical diffraction limit, conventional dielectric lasers with all dimensions in nanoscale are difficult to realize due to the ultimate miniaturization limit of the cavity length and the extremely high requirement of optical gain to overcome the cavity loss. Herein, we have succeeded in reducing the laser size to subwavelength scale in three dimensions using an individual CsPbBr₃ perovskite nanocuboid. Even though the side length of the nanocuboid laser is only ∼400 nm, single-mode Fabry–Pérot lasing at room temperature with laser thresholds of 40.2 and 374 μJ/cm² for one- and two-photon excitation has been achieved, respectively, with the corresponding quality factors of 2075 and 1859. In addition, temperature-insensitive properties from 180 to 380 K have been demonstrated. The physical volume of a CsPbBr₃ nanocuboid laser is only ∼0.49λ³ (where λ is the lasing wavelength in air). Its three-dimensional subwavelength size, excellent stable lasing performance at room temperature, frequency up-conversion ability, and temperature-insensitive properties may lead to a miniaturized platform for nanolasers and integrated on-chip photonic devices in nanoscale

Metabolic and Microbial Profiling of Soil Microbial Community under Per- and Polyfluoroalkyl Substance (PFAS) Stress

Per- and polyfluoroalkyl substances (PFAS) represent significant stress to organisms and are known to disrupt microbial community structure and function. Nevertheless, a detailed knowledge of the soil microbial community responding to PFAS stress at the metabolism level is required. Here we integrated UPLC-HRMS-based metabolomics data with 16S rRNA and ITS amplicon data across soil samples collected adjacent to a fluoropolymer production facility to directly identify the biochemical intermediates in microbial metabolic pathways and the interactions with microbial community structure under PFAS stress. A strong correlation between metabolite and microbial diversity was observed, which demonstrated significant variations in soil metabolite profiles and microbial community structures along with the sampling locations relative to the facility. Certain key metabolites were identified in the metabolite–PFAS co-occurrence network, functioning on microbial metabolisms including lipid metabolism, amino acid metabolism, and secondary metabolite biosynthesis. These results provide novel insights into the impacts of PFAS contamination on soil metabolomes and microbiomes. We suggest that soil metabolomics is an informative and useful tool that could be applied to reinforce the chemical evidence on the disruption of microbial ecological traits

Enhanced Amplified Spontaneous Emission in Quasi-2D Perovskite by Facilitating Energy Transfer

Despite the superior optoelectronic properties of quasi-two-dimensional (quasi-2D) Ruddlesden–Popper halide perovskites, the inhomogeneous distribution of mixed phases result in inefficient energy transfer and multiple emission peaks. Herein, the insufficient energy funneling process at the high-energy phase is almost completely suppressed and the excitonic understanding of gain nature is studied in the energy funneling managed quasi-2D perovskite via introducing poly­(vinyl pyrrolidone) (PVP) additive. The energy transfer process is facilitated from 0.37 to 0.26 ps after introducing the PVP additive, accelerating the exciton accumulation in the emissive state, and increasing the ratio of the high-dimensional phase for enhancing radiative emission. The gain lifetime is promoted to be as fast as 28 ps to outcompete nonradiative recombination during the build-up of population inversion. Simultaneously, the net gain coefficient is increased by more than twofold that of the pristine perovskite film. Owing to the remarkable gain properties, room-temperature amplified spontaneous emission is realized with a low threshold of 11.3 μJ/cm2, 4 times lower than 43 μJ/cm2 of the pristine film. Our findings suggest that the PVP-treated quasi-2D perovskite shows great promise for high-performance laser devices

Probing Molecular-Level Dynamic Interactions of Dissolved Organic Matter with Iron Oxyhydroxide via a Coupled Microfluidic Reactor and an Online High-Resolution Mass Spectrometry System

The interactions between dissolved organic matter (DOM) and iron (Fe) oxyhydroxide are crucial in regulating the biogeochemical cycling of nutrients and elements, including the preservation of carbon in soils. The mechanisms of DOM molecular assembly on mineral surfaces have been extensively studied at the mesoscale with equilibrium experiments, yet the molecular-level evolution of the DOM–mineral interface under dynamic interaction conditions is not fully understood. Here, we designed a microfluidic reactor coupled with an online solid phase extraction (SPE)-LC-QTOF MS system to continually monitor the changes in DOM composition during flowing contact with Fe oxyhydroxide at circumneutral pH, which simulates soil minerals interacting with constant DOM input. Time-series UV–visible absorption spectra and mass spectrometry data showed that after aromatic DOM moieties were first preferentially sequestered by the pristine Fe oxyhydroxide surface, the adsorption of nonaromatic DOM molecules with greater hydrophobicity, lower acidity, and lower molecular weights (<400) from new DOM solutions was favored. This is accompanied by a transition from mineral surface chemistry-dominated adsorption to organic–organic interaction-dominated adsorption. These findings provide direct molecular-level evidence to the zonal model of DOM assembly on mineral surfaces by taking the dynamics of interfacial interactions into consideration. This study also shows that coupled microfluidics and online high-resolution mass spectrometry (HRMS) system is a promising experimental platform for probing microscale environmental carbon dynamics by integrating in situ reactions, sample pretreatment, and automatic analysis

Ultrafast Drift Current Terahertz Emission Amplification in the Monolayer WSe₂/Si Heterostructure

Two-dimensional transition metal dichalcogenides (TMDs) have great potential application for seamless on-chip integration due to their strong photon–electron–spin–valley coupling. However, the contact-free measurements of the valley-coupled photocurrent in TMDs is still challenging. Here, ultrafast terahertz emission spectroscopy is employed to investigate the photocurrent dynamics in monolayer WSe2, and an interface-induced drift current amplification is found in the WSe2/Si heterostructure. The amplification of terahertz emission comes from the photocurrent enlarged by band bending in the WSe2 and Si junction, and the amplification ratio increase further near the valley resonant transition of WSe2. In addition, the valley-momentum locked photocurrent in the WSe2/Si heterostructure reserves the same chirality with monolayer WSe2 at room temperature. These findings could provide a new method for manipulating valley-momentum locked photocurrent by photon helicity and open new avenues for TMD-based valley-polarized terahertz emission devices