Efficient Electrosynthesis of Valuable para-Benzoquinone from Aqueous Phenol on NiRu Hybrid Catalysts.

Electrocatalytic oxidation of aqueous phenol to para-benzoquinone (p-BQ) offers a sustainable approach for both pollutant abatement and value-added chemicals production. However, achieving high phenol conversion and p-BQ yield under neutral conditions remains challenging. Herein, we report a Ni(OH)2-supported Ru nanoparticles (NiRu) hybrid electrocatalyst, which exhibits a superior phenol conversion of 96.5% and an excellent p-BQ yield of 83.4% at pH 7.0, significantly outperforming previously reported electrocatalysts. This exceptional performance benefits from the triple synergistic modulation of the NiRu catalyst, including enhanced phenol adsorption, increased p-BQ desorption, and suppressed oxygen evolution. By coupling a flow electrolyzer with an extraction-distillation separation unit, the simultaneous phenol removal and p-BQ recovery are realized. Additionally, the developed electrocatalytic system with the NiRu/C anode displays good stability, favorable energy consumption, and reduced greenhouse gas emissions for phenol-containing wastewater treatment, demonstrating its potential for practical applications. This work offers a promising strategy for achieving low-carbon emissions in phenol wastewater treatment.

Synergistic Modulation of In-Situ Hybrid Interface Construction and pH Buffering Enabled Ultra-Stable Zinc Anode at High Current Density and Areal Capacity.

In aqueous electrolytes, the uncontrollable interfacial evolution caused by a series of factors such as pH variation and unregulated Zn2+ diffusion would usually result in the rapid failure of metallic Zn anode. Considering the high correlation among various triggers that induce the anode deterioration, a synergistic modulation strategy based on electrolyte modification is developed. Benefitting from the unique pH buffer mechanism of the electrolyte additive and its capability to in situ construct a zincophilic solid interface, this synergistic effect can comprehensively manage the thermodynamic and kinetic properties of Zn anode by inhibiting the pH variation and parasitic side reactions, accelerating de-solvation of hydrated Zn2+ , and regulating the diffusion behavior of Zn2+ to realize uniform Zn deposition. Thus, the modified Zn anode can achieve an impressive lifespan at ultra-high current density and areal capacity, operating stably for 609 and 209 hours at 20 mA cm-2 , 20 mAh cm-2 and 40 mA cm-2 , 20 mAh cm-2 , respectively. Based on this exceptional performance, high loading Zn||NH4 V4 O10 batteries can achieve excellent cycle stability and rate performance. Compared with those previously reported single pH buffer strategies, the synergistic modulation concept is expected to provide a new approach for highly stable Zn anode in aqueous zinc-ion batteries.

Synergistic modulation of surface interaction to assemble metal nanoparticles into two-dimensional arrays with tunable plasmonic properties.

A simple strategy based on the synergistic modulation of inter-particle and substrate-particle interaction is applied for the large-scale fabrication of two-dimensional (2D) Au and Ag nanoparticle arrays. The surface charge of the substrate is used to redistribute the double layer electric charges on the particles and to modulate the inter-particle distance within the 2D nanoparticle arrays on the substrate. The resultant arrays, with a wide range of inter-particle distances, display tunable plasmonic properties. It can be foreseen that such 2D nanoparticle arrays possess potential applications as multiplexed colorimetric sensors, integrated devices and antennas. Herein, it is demonstrated that these arrays can be employed as wavelength-selective substrates for multiplexed acquisition of surface-enhanced Raman scattering (SERS) spectra. This simple one step process provides an attractive and low cost strategy to produce high quality and large area 2D ordered arrays with tunable properties.

Synergistic Modulation of Sn2+ Oxidation and Perovskite Crystallization Induced by 4-Hydroxypyridine for Stable Lead-Free Solar Cells.

Tin perovskites present promising alternatives to lead perovskites, offering comparable optoelectronic properties alongside environmentally friendly characteristics. However, the rapid crystallization and easy oxidation of Sn2+ lead to poor film quality, further constraining the device performance. Here, 4-hydroxypyridine (4-HP) is introduced into the tin perovskite precursor for fabrication of high-quality tin perovskite films. 4-HP could modulate the colloidal size of prenucleation perovskite clusters in the precursor, thus inducing fast nucleation and retarding the crystal growth rate of tin perovskite through the formation of chemical interaction between nitrogen of pyridine and Sn2+ ions. Furthermore, the hydroxyl group on the pyridine ring contributes to suppressing the oxidation of Sn2+. As a result, the power conversion efficiency (PCE) of the devices based on 4-HP increases up to 11.3%. The stability of the unencapsulated devices shows significant improvement, retaining 100% of their initial PCEs after 2000 h of storage in N2 with 50-100 ppm of O2. This research presents a novel approach to the synchronized regulation of tin perovskite crystallization and the suppression of Sn2+ oxidation.

Managing Interfacial Defects and Carriers by Synergistic Modulation of Functional Groups and Spatial Conformation for High-Performance Perovskite Photovoltaics Based on Vacuum Flash Method.

Interfacial nonradiative recombination loss is a huge barrier to advance the photovoltaic performance. Here, one effective interfacial defect and carrier dynamics management strategy by synergistic modulation of functional groups and spatial conformation of ammonium salt molecules is proposed. The surface treatment with 3-ammonium propionic acid iodide (3-APAI) does not form 2D perovskite passivation layer while the propylammonium ions and 5-aminopentanoic acid hydroiodide post-treatment lead to the formation of 2D perovskite passivation layers. Due to appropriate alkyl chain length, theoretical and experimental results manifest that COOH and NH3 + groups in 3-APAI molecules can form coordination bonding with undercoordinated Pb2+ and ionic bonding and hydrogen bonding with octahedron PbI6 4- , respectively, which makes both groups be simultaneously firmly anchored on the surface of perovskite films. This will strengthen defect passivation effect and improve interfacial carrier transport and transfer. The synergistic effect of functional groups and spatial conformation confers 3-APAI better defect passivation effect than 2D perovskite layers. The 3-APAI-modified device based on vacuum flash technology achieves an alluring peak efficiency of 24.72% (certified 23.68%), which is among highly efficient devices fabricated without antisolvents. Furthermore, the encapsulated 3-APAI-modified device degrades by less than 4% after 1400 h of continuous one sun illumination.

Synergistic Modulation between Non-thermal and Thermal Effects in Photothermal Catalysis based on Modified In2O3.

To promote the solar-energy cascade utilization, it is necessary to increase the thermal effect of irradiation in the catalytic reactions, while simultaneously augmenting the non-thermal effect, so as to fulfill photothermal coupling. Herein, the non-thermal and thermal effect of light radiation on the surface of In2O3-based catalysts are explored and enhanced by the modification of transition metals Fe and Cu. Optical characterizations combined with water-splitting experiments show that Fe doping greatly broadens the radiation response range and enhances the absorption intensity of semiconductors' intrinsic portion, and Cu doping facilitates the absorption of visible-infrared light. The concurrent incorporation of Fe and Cu offers synergistic benefits, resulting in improved radiation response range, carrier separation and migration, as well as higher photothermal temperature upon photoexcitation. Collectively, these advantages comprehensively enhance the photothermal synergistic water-splitting reactivity. The characterizations under variable temperature conditions have demonstrated that the reaction temperature exerts a significant influence on the process of radiation absorption and conversion, ultimately impacting the non-thermal effect. The results of DFT calculations have revealed that the increasing temperature directly impacts the chemical reaction by reducing the energy barrier associated with the rate-determining step. These findings shine new light on the fundamental mechanisms underlying non-thermal and thermal effect, while also imparting significant insights for photo-thermal-coupled catalyst designing.

Mutually Tuned Dual Additive Engineering Synergistically Enhances the Photovoltaic Performance of Tin-Based Perovskite Solar Cells.

Tin-based perovskite solar cells (T-PSCs) have become the star photovoltaic products in recent years due to their low environmental toxicity and superior photovoltaic performance. However, the easy oxidation of Sn2+ and the energy level mismatch between the perovskite film and charge transport layer limit its efficiency. In order to regulate the microstructure and photoelectric properties of tin-based perovskite films to enhance the efficiency and stability of T-PSCs, guanidinium bromide (GABr) and organic Lewis-based additive methylamine cyanate (MAOCN) are introduced into the FA0.9PEA0.1SnI3-based perovskite precursor. A series of characterizations show that the interactions between additive molecules and perovskite mutually reconcile to improve the photovoltaic performance of T-PSCs. The introduction of GABr can adjust the band gap of the perovskite film and energy level alignment of T-PSCs. They significantly increase the open-circuit voltage (Voc). The MAOCN material can form hydrogen bonds with SnI2 in the precursor, which can inhibit the oxidation of Sn2+ and significantly improve the short-circuit current density (Jsc). The synergistic modulation of the dual additives reduces the trap-state density and improves photovoltaic performance, resulting in an increased champion efficiency of 9.34 for 5.22% of the control PSCs. The unencapsulated T-PSCs with GABr and MAOCN dual additives prepared in the optimized process can retain more than 110% of their initial efficiency after aging for 1750 h in a nitrogen glovebox, but the control PSCs maintain only 50% of their initial efficiency kept in the same conditions. This work provides a new perspective to further improve the efficiency and stability of T-PSCs.

Optimizing the Nonlinear Optical Performance of an A-N-M-Q (A: Alkali Metal; N: d10 Metal; M: Main Group Metal; Q: Chalcogen) System.

Exploring new infrared nonlinear optical (IR NLO) materials with superior overall properties is scientifically and technically important. However, large second-order harmonic generation (SHG) efficiencies and high laser-induced damage thresholds (LIDT) are incompatible, which makes realizing this goal a challenge. The IR NLO performance of an A-NIIB-MIIIA-Q (Q: chalcogen) system was optimized by simultaneously modulating A/(M + N) and M/N ratios (A: alkali metal; N, M: tetra-coordinated metals), and SHG-LIDT balance was achieved. Three new sulfides, KCd3Ga5S11 (1), RbCd4Ga3S9 (2), and Cs2Cd2Ga8S15 (3), containing the same CdS4 and GaS4 but with different A/(Ga + Cd) and Ga/Cd ratios were obtained. Among these compounds, compound 3 exhibits both the largest SHG efficiency (0.5 × AgGaS2) and LIDT (35 × AgGaS2), which can be ascribed to the Ga/Cd modulation for enhancing the NLO functional motif distortions and SHG efficiency as well as the A/(Ga + Cd) modulation for enlarging the band gap and LIDT. Remarkably, compound 3 is the first phase-matchable IR NLO material in the A-NIIB-MIIIA-Q family. This article proposes a novel avenue to explore infrared nonlinear materials with superior comprehensive properties by modulating the A/(M + N) and M/N ratios.

Dopamine Hydrochloride-Assisted Synergistic Modulation of Perovskite Crystallization and Sn2+ Oxidation for Efficient and Stable Lead-free Solar Cells.

Tin perovskites have received great concern in solar cell research owing to their favorable optoelectronic performance and environmental friendliness. However, due to their poor crystallization and easy oxidation, the performance improvement for tin-based perovskite solar cells (TPSCs) is rather challenging. Herein, reductive 3-hydroxytyramine hydrochloride (DACl) with NH2·HCl and phenol groups as co-additives with SnF2 is added into the precursor to modulate perovskite crystallization and inhibit Sn2+ oxidation for high-performance TPSCs. The Lewis base group of NH2 HCl in DACl could bind to perovskite lattices to modulate the crystallization with suppressed defects in the bulk and grain boundary, whereas reductive phenol groups effectively constrain the Sn2+ oxidation. Moreover, the undissociated DACl decreases the supersaturated concentration of tin perovskite solution and creates a pre-nucleation site for rapid nucleation to further regulate crystallization. Consequently, the DACl-derived TPSCs achieve a high power-conversion efficiency (PCE) that reaches up to 11%. More impressively, the device remains at 84% of the initial PCE after full-sun illumination in N2 over 600 h without being encapsulated. This DACl-based synergistic modulation of a lead-free perovskite demonstrates a feasible approach using one molecule with different functional groups to manipulate crystallization, Sn2+ oxidation, and defect reparation of tin perovskite films, providing a critical guideline for constructing high-quality perovskites by multifunctional additives with high photovoltaic performance.

Ultralow Power Wearable Heterosynapse with Photoelectric Synergistic Modulation.

Although the energy consumption of reported neuromorphic computing devices inspired by biological systems has become lower than traditional memory, it still remains greater than bio-synapses (≈10 fJ per spike). Herein, a flexible MoS2-based heterosynapse is designed with two modulation modes, an electronic mode and a photoexcited mode. A one-step mechanical exfoliation method on flexible substrate and low-temperature atomic layer deposition process compatible with flexible electronics are developed for fabricating wearable heterosynapses. With a pre-spike of 100 ns, the synaptic device exhibits ultralow energy consumption of 18.3 aJ per spike in long-term potentiation and 28.9 aJ per spike in long-term depression. The ultrafast speed and ultralow power consumption provide a path for a neuromorphic computing system owning more excellent processing ability than the human brain. By adding optical modulation, a modulatory synapse is constructed to dynamically control correlations between pre- and post-synapses and realize complex global neuromodulations. The novel wearable heterosynapse expands the accessible range of synaptic weights (ratio of facilitation ≈228%), providing an insight into the application of wearable 2D highly efficient neuromorphic computing architectures.