Unlocking Giant Third-Order Optical Nonlinearity in (MA)2CuX4 through Introducing Jahn-Teller Distortion.

Nonlinear absorption coefficient and modulation depth stand as pivotal properties of nonlinear optical (NLO) materials, while the existing NLO materials exhibit limitations such as low nonlinear absorption coefficients and/or small modulation depths, thereby severely impeding their practical application. Here we unveil that introducing Jahn-Teller distortion in a Mott-Hubbard system, (MA)2CuX4 (MA=methylammonium; X=Cl, Br) affords the simultaneous attainment of a giant nonlinear absorption coefficient and substantial modulation depth. The optimized compound, (MA)2CuCl4, demonstrates a nonlinear absorption coefficient of (1.5±0.08)×105 cm GW-1, a modulation depth of 60 %, and a relatively low optical limiting threshold of 1.22×10-5 J cm-2. These outstanding attributes surpass those of most reported NLO materials. Our investigation reveals that a more pronounced distortion of the [CuX6]4- octahedron emerges as a crucial factor in augmenting optical nonlinearity. Mechanism study involving structural and spectral characterization along with theoretical calculations indicates a correlation between the compelling performance and the Mott-Hubbard band structure of the materials, coupled with the Jahn-Teller distortion-induced d-d transition. This study not only introduces a promising category of high-performance NLO materials but also provides novel insights into enhancing the performance of such materials.

A Review of Ultrathin Piezoelectric Films.

Due to their high electromechanical coupling and energy density properties, ultrathin piezoelectric films have recently been intensively studied as key materials for the construction of miniaturized energy transducers, and in this paper we summarize the research progress. At the nanoscale, even a few atomic layers, ultrathin piezoelectric films have prominent shape anisotropic polarization, that is, in-plane polarization and out-of-plane polarization. In this review, we first introduce the in-plane and out-of-plane polarization mechanism, and then summarize the main ultrathin piezoelectric films studied at present. Secondly, we take perovskite, transition metal dichalcogenides, and Janus layers as examples to elaborate the existing scientific and engineering problems in the research of polarization, and their possible solutions. Finally, the application prospect of ultrathin piezoelectric films in miniaturized energy converters is summarized.

Defect-Dependent Nonlinear Absorption in the Lead-Free Double-Perovskite Cs2AgBiBr6.

Lead-free perovskites have attracted increasing attention because they can address the toxicity and instability problems inherent to lead-halide perovskites. Furthermore, the nonlinear optical (NLO) properties of lead-free perovskites are rarely explored. Herein, we report significant NLO responses and defect-dependent NLO behavior of Cs2AgBiBr6. Specifically, a thin film of pristine Cs2AgBiBr6 exhibits strong reverse saturable absorption (RSA), while a film of Cs2AgBiBr6 with defects (denoted as Cs2AgBiBr6(D)) shows saturable absorption (SA). The nonlinear absorption coefficients are ca. 4.0 × 104 cm GW-1 (515 nm laser excitation) and 2.6 × 104 cm GW-1 (800 nm laser excitation) for Cs2AgBiBr6 and -2.0 × 104 cm GW-1 (515 nm laser excitation) and -7.1 × 103 cm GW-1 (800 nm laser excitation) for Cs2AgBiBr6(D). The optical limiting threshold of Cs2AgBiBr6 is 8.1 × 10-4 J cm-2 (515 nm laser excitation). The samples show excellent long-term performance stability in air. The RSA of pristine Cs2AgBiBr6 correlates with excited-state absorption (515 nm laser excitation) and excited-state absorption following two-photon absorption (800 nm laser excitation), while the defects in Cs2AgBiBr6(D) strengthen the ground-state depletion and Pauli blocking, resulting in SA.

Spatial Compartmentalization of Cobalt Phosphide in P-Doped Dual Carbon Shells for Efficient Alkaline Overall Water Splitting.

Highly durable and earth-abundant bifunctional catalysts with low cell voltage are desirable for alkaline overall water splitting in the industrial fields. Herein, a novel carbon-based CoP hybrid with spatial compartmentalization of CoP nanoparticles (NPs) in P-doped dual carbon shells is achieved via a cheap Co-glycerate-template strategy. Benefitted from the uniform atomic blending of Co2+ ions in the Co-glycerate precursors, CoP NPs in situ formed in the confined space with NaH2PO2 as phosphorus source during the annealing process; meanwhile, glycerate suffered carbonization and transformed into P-doped dual carbon shells during the annealing process, including interior thin carbon coating, closely encircled CoP NP, and peripheral hollow carbon sphere loading a lot of CoP NPs. Not only does spatial compartmentalization of CoP NPs avoid the aggregation and expose more active sites but also P-doped dual carbon shells improve the conductivity and durability of the catalyst. As expected, the optimized hybrid exhibits outstanding electrocatalytic activities in alkaline media, such as hydrogen evolution reaction (HER) overpotential of 101 mV, oxygen evolution reaction (OER) overpotential of 280 mV, and a low cell voltage of 1.66 V to deliver a current density of 10 mA cm-2. Moreover, durability and stability are greatly improved under harsh electrochemical conditions. The current strategy shades new insight into the development of carbon-based transition metal phosphides (TMP) catalysts for electrocatalysis applications.

Ti3+ self-doped TiO2-x nanowires for efficient electrocatalytic N2 reduction to NH3.

Electrochemical N2 reduction is an environmentally friendly and sustainable approach for NH3 synthesis under mild conditions, while an efficient electrocatalyst is crucial for the N2 reduction reaction (NRR). Herein, we report Ti3+ self-doped TiO2-x nanowires on Ti mesh (Ti3+-TiO2-x/TM) as an efficient non-noble-metal NRR electrocatalyst with excellent selectivity. In 0.1 M Na2SO4, the Ti3+-TiO2-x/TM achieves a high faradaic efficiency of 14.62% with a NH3 yield of 3.51 × 10-11 mol s-1 cm-2 at -0.55 V vs. the reversible hydrogen electrode. Density functional theory calculations further reveal that introducing Ti3+ decreases the reaction energy barrier and increases the number of active sites on the TiO2 surface for the NRR.

A perovskite La2Ti2O7 nanosheet as an efficient electrocatalyst for artificial N2 fixation to NH3 in acidic media.

The synthesis of NH3 heavily relies on the Haber-Bosch process suffering from a large amount of CO2 emission and energy consumption. Possessing eco-friendly and sustainable characteristics, electrochemical reduction is considered as a promising candidate for artificial N2 fixation under ambient conditions, but efficient electrocatalysts are crucial for the N2 reduction reaction (NRR). In this communication, we report that perovskite La2Ti2O7 nanosheets behave as an efficient NRR electrocatalyst with excellent selectivity under ambient conditions. In 0.1 M HCl, this catalyst achieves a high NH3 yield rate of 25.15 µg h-1 mgcat.-1 with a faradaic efficiency of 4.55% at -0.55 V vs. a reversible hydrogen electrode. Notably, it also shows high electrochemical stability.

Platinum-Copper Bimetallic Alloy Nanoflowers as Efficient Electrocatalyst for the Methanol Oxidation Reaction.

Special morphological noble metal-based bimetallic alloy nanostructures became popular for methanol oxidation reaction in order to reduce the high cost of the Pt catalyst and improve the catalyst activity. Herein, we developed a facile one pot hydrothermal method for the synthesis of platinum-copper bimetallic nanoflowers (Pt-Cu NFs) in the presence of hexadecyl trimethyl ammonium bromide (CTAB). The morphology, structure and composition of Pt-Cu NFs were carefully characterized and the synthesized parameters were optimized systematically by adjusting different experimental conditions. Results showed that the CTAB usage and the NaI amount were critical to the controlled synthesis of Pt-Cu NFs. The Pt-Cu NFs were high-performance electrocatalysts for the methanol oxidation reaction (MOR) with superior activity and superior stability in alkaline solution, which were far better than pure Pt nanoparticle electrocatalysts.