Tuning the Work Function of MXene via Surface Functionalization.

MXenes, a class of two-dimensional materials, have garnered significant attention due to their versatile surface chemistry and customizable properties. In this study, we investigate the work function (WF) tuning capabilities of MXene Ti3C2Tx, where Tx denotes the surface termination, synthesized via both conventional hydrogen fluoride-etched and recently reported molten salt-etched routes. When MXene samples are subjected to gas phase reactions, WF variations exceeding 0.6 eV are achieved, highlighting the potential for precise WF control. Notably, the WF increases from ∼4.23 eV (in N-doped MXene etched using molten salt) to ∼4.85 eV (N-doped MXene etched using HF). Complementary density functional theory (DFT) calculations reveal WF tuning across a >1 eV range via modification of the surface with different terminal groups (bare metal, F*, O*, N*, and Cl*). These changes in WF are attributed to surface termination modifications and the formation of TiO2 and TiN phases during annealing. DFT calculations further unveil an inverse correlation between the WF and the electron affinity of surface terminations. The findings from this comprehensive study provide insights into the tunable WF of MXenes, paving the way for their potential applications as interfacial layers in photovoltaic, energy conversion, and storage technologies.

Additive manufacturing of alloys with programmable microstructure and properties.

In metallurgy, mechanical deformation is essential to engineer the microstructure of metals and to tailor their mechanical properties. However, this practice is inapplicable to near-net-shape metal parts produced by additive manufacturing (AM), since it would irremediably compromise their carefully designed geometries. In this work, we show how to circumvent this limitation by controlling the dislocation density and thermal stability of a steel alloy produced by laser powder bed fusion (LPBF) technology. We show that by manipulating the alloy's solidification structure, we can 'program' recrystallization upon heat treatment without using mechanical deformation. When employed site-specifically, our strategy enables designing and creating complex microstructure architectures that combine recrystallized and non-recrystallized regions with different microstructural features and properties. We show how this heterogeneity may be conducive to materials with superior performance compared to those with monolithic microstructure. Our work inspires the design of high-performance metal parts with artificially engineered microstructures by AM.

Two-Dimensional Palladium Phosphoronitride for Oxygen Reduction.

Two-dimensional (2D) catalysts often show extraordinary activity at low mass loading since almost all their atoms are exposed to electrolyte. Palladium (Pd) holds great promise for catalyzing oxygen reduction reaction (ORR) but 2D Pd-based ORR catalyst has rarely been reported. Herein, 2D ternary palladium phosphoronitride (Pd3P2Nx) is synthesized, for the first time, for ORR catalysis. The synthesis is guided by a rational design using first-principles density functional theory calculations, and then realized via a postsynthesis substitutional doping of ternary palladium thiophosphate (Pd3P2S8), which almost completely replaces sulfur atoms by nitrogen atoms without destroying the 2D morphology. The doping process exposes the interlocked Pd atoms of Pd3P2S8 and introduces ligands that improve the affinity of oxygen intermediates, resulting in greater kinetics and lower activation energy for ORR. The mass activity of the pristine Pd3P2S8 is dramatically increased as much as 5-fold (from 0.03 to 0.151 mA µg-1 Pd in Pd3P2Nx). The ORR diffusion-limited current density of Pd3P2Nx (6.2 mA cm-2) exceeds that of commercial Pt/C, and it shows fast kinetics and robust long-term stability. Our theoretical calculations not only guide the experimental doping process, but also provides insights into the underlying mechanism of the outstanding ORR activity and stability.

Low-Power Magnetron Sputtering Deposition of Antimonene Nanofilms for Water Splitting Reaction.

Antimonene (Sb) is a novel kind of two-dimensional (2D) material that is predicted to be promising for various applications, such as water splitting and semiconductor devices. Several methods have been reported to prepare Sb nanoflakes/nanofilms; however, it is still relatively difficult to prepare Sb nanofilms. In this work, a method of low-power magnetron sputtering deposition was used for the preparation of Sb nanofilms with lateral dimensions on the centimeter scale and controllable film thickness. It was found that the control of the deposition temperature is important for the final crystalline structure of the nanofilms. Furthermore, the application of the nanofilms as a catalyst for water splitting (hydrogen evolution reaction (HER) and oxygen evolution reaction (OER)) was demonstrated.

Porous silver microrods by plasma vulcanization activation for enhanced electrocatalytic carbon dioxide reduction.

Metal electrode is considered as an ideal candidate for electrocatalytic carbon dioxide (CO2) reduction considering its excellent chemical stability, application potential and eco-friendly properties. Optimization process such as morphological control, non-metallic doping, alloying is widely studied to improve the efficiency of metal electrodes. In this work, we successfully improved the CO2 reduction performance of silver using a facile plasma vulcanization treatment. The obtained sulfide derived silver (Ag) porous microrods (SD-AgPMRs) are optimized from both morphology and composition aspects, and demonstrates high Faradaic efficiency and partial current density for carbon monoxide (CO) production at low potentials. The larger specific surface area of porous microrod structure and the improved adsorption energy of important intermediates in comparison with Ag foil are realized by introduction of sulfur (S) atoms after plasma vulcanization activation, as suggested by density functional theory (DFT) calculations. This work presents a novel strategy to optimize metal electrocatalysts for CO2 reduction as well as to improve catalysis in other fields.

Pseudo-magnetic field-induced slow carrier dynamics in periodically strained graphene.

The creation of pseudo-magnetic fields in strained graphene has emerged as a promising route to investigate intriguing physical phenomena that would be unattainable with laboratory superconducting magnets. The giant pseudo-magnetic fields observed in highly deformed graphene can substantially alter the optical properties of graphene beyond a level that can be feasible with an external magnetic field, but the experimental signatures of the influence of such pseudo-magnetic fields have yet to be unveiled. Here, using time-resolved infrared pump-probe spectroscopy, we provide unambiguous evidence for slow carrier dynamics enabled by the pseudo-magnetic fields in periodically strained graphene. Strong pseudo-magnetic fields of ~100 T created by non-uniform strain in  graphene on nanopillars are found to significantly decelerate the relaxation processes of hot carriers by more than an order of magnitude. Our findings offer alternative opportunities to harness the properties of graphene enabled by pseudo-magnetic fields for optoelectronics and condensed matter physics.

Mechanistic Investigation of Electrostatic Field-Enhanced Water Evaporation.

Investigations on external electrostatic field (EEF)-enhanced liquid water evaporation have been reported decades ago, which suggest that molecular alignment and polarization tuned by EEF accelerating the phase change process could be responsible for EEF-enhanced water evaporation. However, a detailed study revealing the role of EEF in altering the intermolecular and intramolecular water structure is lacking. Herein, an EEF is proved to tune water state by accelerating the thermal movement of water molecules, lowering the molecular escaping energy, and loosening the hydrogen bond structure. The detailed mechanisms and field interactions (heat and electrostatic) are investigated by in situ Raman characterizations and molecular dynamic simulations, which reveal that an EEF can effectively reduce the free energy barrier of water evaporation and then increase the evaporated water molecule flux. As a proof of concept, an EEF is integrated into an interfacial two-dimentional solar steam generator, enhancing the efficiency by up to 15.6%. Similar to a catalyst lowing activation energy and enhancing kinetics of a chemical reaction, the EEF enhances water state tuning, lowers evaporation enthalpy, and then boosts steam generation rate with negligible additional energy consumption, which can serve as a generic method for water evaporation enhancement in water harvesting, purification, and beyond.

Rapid fabrication of complex nanostructures using room-temperature ultrasonic nanoimprinting.

Despite its advantages of scalable process and cost-effectiveness, nanoimprinting faces challenges with imprinting hard materials (e.g., crystalline metals) at low/room temperatures, and with fabricating complex nanostructures rapidly (e.g., heterojunctions of metal and oxide). Herein, we report a room temperature ultrasonic nanoimprinting technique (named nanojackhammer) to address these challenges. Nanojackhammer capitalizes on the concentration of ultrasonic energy flow at nanoscale to shape bulk materials into nanostructures. Working at room temperature, nanojackhammer allows rapid fabrication of complex multi-compositional nanostructures made of virtually all solid materials regardless of their ductility, hardness, reactivity and melting points. Atomistic simulations reveal a unique alternating dislocation generation and recovery mechanism that significantly reduces the imprinting force under ultrasonic cyclic loading. As a proof-of-concept, a metal-oxide-metal plasmonic nanostructure with built-in nanogap is rapidly fabricated and employed for biosensing. As a fast, scalable, and cost-effective nanotechnology, nanojackhammer will enable various unique applications of complex nanostructures in optoelectronics, biosensing, catalysis and beyond.