Amine Coordinated Electron-Rich Palladium Nanoparticles for Electrochemical Hydrogenation of Benzaldehyde

Electrocatalytic hydrogenation (ECH) is a burgeoning strategy for the sustainable utilization of hydrogen. However, how to effectively suppress the competitive hydrogen evolution reaction (HER) is a big challenge to ECH catalysis. In this study, amine (NH₂ R)-coordinated Pd nanoparticles loaded on carbon felt (Pd@CF) as a catalyst is successfully synthesized by a one-step solvothermal reduction method using oleylamine as the reducing agent. An exceptional ECH reactivity on benzaldehyde is achieved on the optimal Pd@CF catalyst in terms of a high conversion (89.7%) and selectivity toward benzyl alcohol (89.8%) at −0.4 V in 60 min. Notably, the Faradaic efficiency for producing benzyl alcohol is up to 90.2%, much higher than that catalyzed by Pd@CF-without N-group (41.1%) and thecommercial Pd/C (20.9%). The excellent ECH performance of Pd@CF can be attributed to the enriched electrons on Pd surface resulted from the introduction of NH₂ R groups, which strengthens both the adsorption of benzaldehyde and the adsorbed hydrogen (H_ads) on Pd, preventing the combination of H_ads to form H₂, that is, inhibiting the HER. This study gives a new insight into design principles of highly efficient electrocatalysts for the hydrogenation of unsaturated aldehydes molecules.     

Balancing MXene Surface Termination and Interlayer Spacing Enables Superior Microwave Absorption

Surface chemistry and interlayer engineering determines the electrical properties of 2D MXene. However, it remains challenging to regulate the surface and interfacial chemistry of MXene simultaneously. Herein, simultaneous modulation of Ti₃C₂T_x MXene surface termination and layer spacing by alkali treatment are achieved. The electrical and electromagnetic properties of Ti₃C₂T_x are investigated in detail with respect to KOH and ammonia concentration dependence. A high concentration of KOH caused the Ti₃C₂T_x layer spacing to expand to 13.7 Å and the surface O/F ratio to increase to 33.84. Because of its weaker ionization effect, ammonia provides finer tuning compared to the drastic intercalation of KOH with a thorough sweeping of the F-containing groups. Ti₃C₂T_x is enriched with conductive -OH termination after ammonia treatment, which achieves an effective balance with the increased interlayer resistance. Therefore, NH₃H₂O-Ti₃C₂T_x achieves broad-band impedance matching and exhibits an efficient microwave loss of −49.1 dB at a low thickness of 1.7 mm, with an effective frequency bandwidth of 3.9 GHz. The results herein optimize the electrical properties of Ti₃C₂T_x using surface and interfacial chemistry to achieve broad microwave absorption, providing a framework for enhancing the electromagnetic wave loss of intrinsic MXene.     

Reaching the Fundamental Limitation in CO2 Reduction to CO with Single Atom Catalysts

The electrochemical CO₂ reduction reaction (CO₂RR) to value-added chemicals with renewable electricity is a promising method to decarbonize parts of the chemical industry. Recently, single metal atoms in nitrogen-doped carbon (MNC) have emerged as potential electrocatalysts for CO₂RR to CO with high activity and faradaic efficiency, although the reaction limitation for CO₂RR to CO is unclear. To understand the comparison of intrinsic activity of different MNCs, two catalysts are synthesized through a decoupled two-step synthesis approach of high temperature pyrolysis and low temperature metalation (Fe or Ni). The highly meso-porous structure results in the highest reported electrochemical active site utilization based on in situ nitrite stripping; up to 59±6% for NiNC. Ex situ X-ray absorption spectroscopy (XAS) confirms the penta-coordinated nature of the active sites. The catalysts are amongst the most active in the literature for CO₂ reduction to CO. The density functional theory calculations (DFT) show that their binding to the reaction intermediates approximates to that of Au surfaces. However, it is found that the turnover frequencies (TOFs) of the most active catalysts for CO evolution converge, suggesting a fundamental ceiling to the catalytic rates.     

Exploring a Stable and Dense 3D Lead Chloride Hybrid with Emission of Self-Trapped Excitons toward X-Ray Scintillation

The exceptional photophysical properties of 3D organic–inorganic lead halide hybrids (OILHs) endow their significant potential for usage in optoelectronics, which has sparked intense research on novel 3D OILHs and associated applications. However, constructing new 3D OILHs based on large organic cations suffers from tough challenges due to the limitation of the Goldschmidt tolerance factor rule, let alone further explorations of their practical applications. Herein, a brand-new 3D lead chloride hybrid, (1MPZ)Pb₄Cl₁₀·H₂O ( 1 , 1MPZ = 1-methylpiperazine) is reported, featuring a dense 3D lead chloride framework made of the corner-, edge-, and face-shared lead chloride polyhedra. 1 presents a broadband white light emission with a large Stokes shift and a nanosecond photoluminescence lifetime, which originates from radiative recombination of self-trapped excitons (STEs) induced by the highly distorted structure. Such a reabsorption-free and fast-decayed STEs emission coupling with the dense 3D architecture further enables 1 with effective X-ray scintillation with good sensitivity. Impressively, 1 also shows superior environmental and radiation stability. This study provides a new 3D OILH with appealing luminescence, not only expanding the 3D OILH family but also inspiring the exploitation of their optoelectronic applications.     

Paving the Way for High-Performance UVB-LEDs Through Substrate-Dominated Strain-Modulation

AlGaN-based ultraviolet-B light-emitting diodes (UVB-LEDs) exhibit great potential in phototherapy, vitamin D3 synthesis promotion, plant growth regulation, and so on. However, subjected to the excess compressive strain induced by the large lattice mismatch between multiple quantum wells (MQWs) and AlN, UVB-LEDs that simultaneously satisfy the requirements of high light output power (LOP), low working voltage, and excellent stability are rarely reported. Here, a substrate-dominated strain-modulation strategy is proposed. By precisely manipulating the strain in AlN grown on nano-patterned sapphire substrate (NPSS) to a slightly tensile one, the compressive strain in the following Al_0.55Ga_0.45N underlayer and Al_0.28Ga_0.72N/Al_0.45Ga_0.55N MQWs is successfully suppressed. As a result, an outstanding UVB-LED with a peak wavelength at 303.6 nm is achieved. The 20 × 20 mil² UVB-LED chip shows a wall-plug efficiency (WPE) of 3.27% under a forward current of 20 mA and a high LOP of 57.2 mW with an extremely low voltage of 5.87 V under a forward current of 800 mA. It is more exciting that the LOP degradation is as low as 17% after 1000 h operation under a forward current density of 75 A cm⁻², showing excellent stability. The here-developed UVB-LED, with a high LOP and excellent reliability, will definitely promote the applications of AlGaN-based UVB-LEDs.     

All-Visible-Light Triggered Photoswitch of Dithienylethene Derivatives with Molecular Conformation Changes Excess 5 Å

Developing new all-visible-light driven fluorescent molecular switches has attracted much interests due to their important application prospects in materials science and life science. Herein, three novel all-visible-light triggered fluorescent molecular photoswitches ( 2P3 , 4F , and 4Cl ) are designed and prepared, which are realized by prolonging π-conjugation length with aggregated-induced emission units. These photoswitches show reversible photochromic and fluorescent switching in dilute solutions and films under 420 nm and 560 nm irradiations. Meanwhile, upon alternating irradiations with 450 nm/560 nm light, effective photochromic and fluorescent switching in powder states are also achieved. More interestingly, two distinct conformations with different photochromic abilities can be altered by solvents polarity. The size difference of the two conformations is over 5 Å in the vertical direction which is one of the largest changes among photochromic molecules based on dithienylethene. The accompanying conformational changes are analysed to understand the relationship between solvent characteristics and crystal structure, as well as the intermolecular interaction in solid state for all-visible-light triggered photoswitching molecules.     

Thermally Responsive Fibers for Versatile Thermoactivated Protective Fabrics

Smart textiles with good mechanical adaptability play an important role in personal protection, health monitoring, and aerospace applications. However, most of the reported thermally responsive polymers has long response time and poor processability, comfort, and wearability. Skin-core structures of thermally responsive fibers with multiple commercial fiber cores and temperature-responsive hydrogel skins are designed and fabricated, which exhibit rapid mechanical adaptability, good thermohardening, and thermal insulation. This universal method enables tight bonding between various commercial fiber cores and hydrogel skins via specific covalently anchored networks. At room temperature, prepared fibers show softness, flexibility, and skin compatibility similar to those of ordinary fibers. As temperature rises, smart fibers become hard, rigid, and self-supporting. The modulus of hydrogel skin increases from 304% to 30883%, showing good mechanoadaptability and impact resistance owing to the synergy between hydrophobic interactions and ionic bonding. Moreover, this synergistic effect leads to an increase in heat absorption, and fibers exhibit good thermal insulation, which reduces the contact temperature of the body surface by ≈25 °C under the external temperature of 95 °C, effectively preventing thermal burns. Notably, the active mechanoadaptability of these smart fibers using conductive fibers as cores is demonstrated. This study provides feasibility for fabricating environmentally adaptive intelligent textiles.     

Marine-Derived Hydrogels for Biomedical Applications

Marine organisms provide novel and broad sources for the preparations and applications of biomaterials. Since the urgent requirement of bio-hydrogels to mimic tissue extracellular matrix (ECM), the natural biomacromolecule hydrogels derived from marine sources have received increasing attention. Benefiting from their outstanding bioactivity and biocompatibility, many attempts have been made to reconstruct ECM components by applying marine-derived natural hydrogels. Moreover, marine hydrogels have been successfully applied in biomedicine by means of microfluidics, electrospray, and bioprinting. In this review, the classification and characteristics of marine-derived hydrogels are summarized. In particular, their role in the development of biomaterials is also introduced. Then, the recent advances in bio-fabrication strategies for various hydrogel materials are focused upon. Besides, the influences of hydrogel types on their functions in biomedical applications are discussed in depth. Finally, critical reflections on the limitations and future development of marine-derived hydrogels are presented.     

Breaking the Responsivity-Bandwidth Trade-Off Limit in GaN Photoelectrodes for High-Response and Fast-Speed Optical Communication Application

Underwater optical communication (UOC) has attracted considerable interest in the continuous expansion of human activities in marine/ocean environments. The water-durable and self-powered photoelectrodes that act as a battery-free light receiver in UOC are particularly crucial, as they may directly face complex underwater conditions. Emerging photoelectrochemical (PEC)-type photodetectors are appealing owing to their intrinsic aqueous operation characteristics with versatile tunability of photoresponses. Herein, a self-powered PEC photodetector employing n-type gallium nitride (GaN) nanowires as a photoelectrode, which is decorated with an iridium oxide (IrO_x) layer to optimize charge transfer dynamics at the GaN/electrolyte interface, is reported. Strikingly, the constructed n-GaN/IrO_x photoelectrode breaks the responsivity-bandwidth trade-off limit by simultaneously improving the response speed and responsivity, delivering an ultrafast response speed with response/recovery times of only 2 µs/4 µs while achieving a high responsivity of 110.1 mA W⁻¹. Importantly, the device exhibits a large bandwidth with 3 dB cutoff frequency exceeding 100 kHz in UOC tests, which is one of the highest values among self-powered photodetectors employed in optical communication system.     

Dispersion-Enabled Symmetry Switching of Photonic Angular-Momentum Coupling

Photonic spin-orbit interactions describe the interactions between spin angular momentum and orbital angular momentum of photons, which play essential roles in subwavelength optics. However, the influence of frequency dispersion on photonic angular-momentum coupling is rarely studied. Here, by elaborately designing the contribution of the geometric phase and waveguide propagation phase, the dispersion-enabled symmetry switching of photonic angular-momentum coupling is experimentally demonstrated. This notion may induce many exotic phenomena and be found in enormous applications, such as the spin-Hall effect, optical calculation, and wavelength division multiplexing systems. As a proof-of-concept demonstration, two metadevices, a multi-channel vectorial vortex beam generator and a phase-only hologram, are applied to experimentally display optical double convolution, which may offer additional degrees of freedom to accelerate computing and a miniaturization configuration for optical convolution without collimation operation. These results may provide a new opportunity for complex vector optical field manipulation and calculation, optical information coding, light-matter interaction manipulation, and optical communication.