Boosting Solar-Driven CO2 Conversion to Ethanol via Single-Atom Catalyst with Defected Low-Coordination Cu-N2 Motif.

In this paper, we report a high-performance carbon nitride supported Cu single-atom catalyst featuring defected low-coordination Cu-N2 motif (Cu-N2-V). Lead many recently reported photocatalysts and its Cu-N3 and Cu-N4 counterparts, Cu-N2-V exhibits superior photocatalytic activity for CO2 reduction to ethanol, delivering 69.8 µmol g-1 h-1 ethanol production rate, 97.8% electron-based ethanol selectivity, and a yield of ~10 times higher than Cu-N3 and Cu-N4. Revealed by the extensive experimental investigation combined with the DFT calculation, the superior photoactivity of Cu-N2-V stems from its unique defected Cu-N2 configuration. Firstly, Cu in Cu-N2-V exist in Cu+/Cu2+ dual valence states, although predominantly in Cu+. The Cu+ sites support CO2 activation and the Cu+/Cu2+ sites are conducive for strong *CO adsorption and subsequent *CO-*CO dimerization enabling C-C coupling. Secondly, the Cu sites in Cu-N2-V are rich in electrons and thus highly active. Together they dictate the rate-determining step on CO2 photoreduction to ethanol and lower the Gibbs free energy change. Furthermore, the defected configuration also promotes light adsorption and charge separation efficiency. Collectively, these make Cu-N2-V an effective and high-performance catalyst for solar-driven CO2 conversion to ethanol. This study also reveals the valence state change of Cu in Cu-N2-V during the CO2 photoreduction reaction.

Redox-induced controllable engineering of MnO2-MnxCo3-xO4 interface to boost catalytic oxidation of ethane.

Multicomponent oxides are intriguing materials in heterogeneous catalysis, and the interface between various components often plays an essential role in oxidations. However, the underlying principles of how the hetero-interface affects the catalytic process remain largely unexplored. Here we report a unique structure design of MnCoOx catalysts by chemical reduction, specifically for ethane oxidation. Part of the Mn ions incorporates with Co oxides to form spinel MnxCo3-xO4, while the rests stay as MnO2 domains to create the MnO2-MnxCo3-xO4 interface. MnCoOx with Mn/Co ratio of 0.5 exhibits an excellent activity and stability up to 1000 h under humid conditions. The synergistic effects between MnO2 and MnxCo3-xO4 are elucidated, in which the C2H6 tends to be adsorbed on the interfacial Co sites and subsequently break the C-H bonds on the reactive lattice O of MnO2 layer. Findings from this study provide valuable insights for the rational design of efficient catalysts for alkane combustion.

Suppressing Metal Leaching and Sintering in Hydroformylation Reaction by Modulating the Coordination of Rh Single Atoms with Reactants.

Hydroformylation reaction is one of the largest homogeneously catalyzed industrial processes yet suffers from difficulty and high cost in catalyst separation and recovery. Heterogeneous single-atom catalysts (SACs), on the other hand, have emerged as a promising alternative due to their high initial activity and reasonable regioselectivity. Nevertheless, the stability of SACs against metal aggregation and leaching during the reaction has rarely been addressed. Herein, we elucidate the mechanism of Rh aggregation and leaching by investigating the structural evolution of Rh1@silicalite-1 SAC in response to different adsorbates (CO, H2, alkene, and aldehydes) by using diffuse reflectance infrared Fourier transform spectroscopy, X-ray adsorption fine structure, and scanning transmission electron microscopy techniques and kinetic studies. It is discovered that the aggregation and leaching of Rh are induced by the strong adsorption of CO and aldehydes on Rh, as well as the reduction of Rh3+ by CO/H2 which weakens the binding of Rh with support. In contrast, alkene effectively counteracts this effect by the competitive adsorption on Rh atoms with CO/aldehyde, and the disintegration of Rh clusters. Based on these results, we propose a strategy to conduct the reaction under conditions of high alkene concentration, which proves to be able to stabilize Rh single atom against aggregation and/or leaching for more than 100 h time-on-stream.

Synergistic cobalt­copper metal-organic framework anchored amino-functionalized cellulose for antibiotic degradation: Interfacial engineering and mechanism insight.

Improving electron transfer rate of Co species and inhibiting aggregation of metal-organic frameworks (MOFs) particles are essential prerequisites for activating advanced oxidation process in wastewater treatment field. Here, we exploit Cu species with variable valence states to accelerate electron transfer of Co species and then to boost the unsatisfactory degradation efficiency for refractory pharmaceuticals via in-situ growth of copper and cobalt species on l-lysine functionalized carboxylated cellulose nanofibers. Utilizing the synergistic interplay of Co sites and deliberately exposed Cu0/Cu1+ atoms, the subtly designed catalyst exhibited a surprising degradation efficiency (~100 %) toward tetracycline hydrochloride within 10 min (corresponding to a catalytic capacity of 267.71 mg/g) without adjusting temperature and pH. Meanwhile, the catalyst displays good recyclability, well tolerance for coexisting ions and excellent antibacterial performance derived from the intrinsic antibacterial property of Cu-MOF. This research provided a novel strategy to construct MOFs-cellulose materials toward degrading various stubborn antibiotic pollutants.

Atomic scale analysis of Zn2+ storage in robust tunnel frameworks.

Realizing rapid and reversible Zn2+ storage at the cathode is imperative for the advancement of aqueous Zn-ion batteries (ZIBs), which offer an excellent option for large-scale electrochemical energy storage. However, owing to limitations of the structural stability of previously investigated frameworks, the Zn2+ storage processes remain unclear, thus hindering progress towards the above goal. Herein, we present the novel application of MoVTe oxide with an M1 phase (MVT-M1) as a potential cathode material for ZIBs. MVT-M1 features broad and robust tunnels that facilitate reversible Zn2+ insertion/extraction during cycling, as well as rich redox centers (Mo, V, and Te) to aid in charge redistribution, resulting in good performances in ZIBs. The exceptional resilience of MVT-M1 to high-energy electron beams allows for direct observation of Zn2+ insertion/extraction at the atomic scale within the tunnels for the first time using high-angle annular dark field scanning transmission electron microscopy; the storage location of zinc ions within the cathode is accurately determined layer by layer from the surface to the bulk phase by employing time-of-flight secondary ion mass spectrometry. Additionally, solvent molecules (H2O and methanol) are also found inside the tunnels along with Zn2+. Due to the broader heptagonal tunnels and Te ions in the hexagonal tunnels, MVT-M1 exhibits good cycling stability, outperforming MoVTe oxide with the M2 phase (no heptagonal tunnels) and MoV oxide with the M1 phase (no Te). These findings hold significant importance in advancing our understanding of the Zn2+ storage mechanism and enable the design of novel materials specifically optimized for efficient Zn2+ storage.

Disentangling the activity-selectivity trade-off in catalytic conversion of syngas to light olefins.

Breaking the trade-off between activity and selectivity has been a long-standing challenge in the field of catalysis. We demonstrate the importance of disentangling the target reaction from the secondary reactions for the case of direct syngas conversion to light olefins by incorporating germanium-substituted AlPO-18 within the framework of the metal oxide-zeolite (OXZEO) catalyst concept. The attenuated strength of the catalytically active Brønsted acid sites allows enhancing the targeted carbon-carbon coupling of ketene intermediates to form olefins by increasing the active site density while inhibiting secondary reactions that consume the olefins. Thus, a light-olefins selectivity of 83% among hydrocarbons and carbon monoxide conversion of 85% were obtained simultaneously, leading to an unprecedented light-olefins yield of 48% versus current reported light-olefins yields of ≤27%.

Insight into the Evolution Track for the Metathesis of Alkenes within Hierarchical Zeolite-Based Catalysts.

The usage of hierarchical MFI zeolite enables a boost of the catalytic performance of Mo-based catalysts for the olefin-metathesis reaction. The harvest of active catalysts roots in a segmental evolution track between hierarchical zeolite and Al2 O3 slices for the fabrication of active sites. The working evolution track requires the indispensable engagements from intracrystalline mesoporous surface, Al2 O3 slices, and zeolitic Brønsted acid sites. The infilling of disaggregated Al2 O3 slices into the intracrystalline mesopores triggers the creation of localized intrazeolite-Al2 O3 interfaces, which enables the subsequent migration and trapping of surface molybdates into the micropores. The insulation of intrazeolite-Al2 O3 interface or shielding of zeolitic Brønsted acid sites leads to the break of the evolution track. Our findings disclose the hidden functionality of mesoporosity as intrazeolite interface boundary for the fabrication of active sites and supply a new strategy for the rational design of zeolite catalysts.

Precise Drift Tracking for In Situ Transmission Electron Microscopy via a Thon-Ring Based Sample Position Measurement.

Visualizing how a catalyst behaves during chemical reactions using in situ transmission electron microscopy (TEM) is crucial for understanding the activity origin and guiding performance optimization. However, the sample drifts as temperature changes during in situ reaction, which weakens the resolution and stability of TEM imaging, blocks insights into the dynamic details of catalytic reaction. Herein, a Thon-ring based sample position measurement (TSPM) was developed to track the sample height variation during in situ TEM observation. Drifting characteristics for three commercially available nanochips were studied, showing large biases in aspects of shifting modes, expansion heights, as well as the thermal conduction hysteresis during rapid heating. Particularly, utilizing the TSPM method, for the first time, the gas layer thickness inside a gas-cell nanoreactor was precisely determined, which varies with reaction temperature and gas pressure in a linear manner with coefficients of ~8 nm/°C and ~50 nm/mbar, respectively. Following drift prediction of TSPM, fast oxidation kinetics of a Ni particle was tracked in real time for 12 s at 500°C. This TSPM method is expected to facilitate the functionality of automatic target tracing for in situ microscopy applications when feedback to hardware control of the microscope.

Dynamics of the charging-induced imaging instability in transmission electron microscopy.

Revolutionary microscopy technologies for aberration correction in spatial and energy aspects have exhibited continuous progress, pushing forward the information limit of materials research down to a scale of sub-angstrom and milli-electron voltage. Nevertheless, imaging quality could still suffer due to sample instability, e.g. the charging effect, which always comes along with electron microscopy characterizations. Herein, using a defocus estimation algorithm and an in situ image feature tracking method, we quantitatively studied the image drifting dynamics induced by the charging on transmission electron microscopy (TEM) carrier grids with tunable electrical conductivity. Experimental evidence clarifies the debate about the charge types, proving that the irradiation of the electron beam induces a positive charge on the grid sample of poor electrical conductivity. Such charge accumulation accounts for subsequent imaging instability, including the increase of defocus and the drift of lateral images. Particularly, the competition between charging and discharging was found to dynamically modulate the propagation of electron beam, resulting in a periodically reciprocating movement on TEM images. These findings enrich understanding on the dynamic principle of charging effects as well as the details of image drifting behaviors. It also suggests specific attention on the importance of conductivity control on a TEM specimen, beyond all the efforts for instrumental improvements.