Amorphous noble metals exhibit unique electronic properties due to their disordered atomic structures; however, their potential in photothermal therapy (PTT) remains largely unexplored. This limitation arises primarily from difficulties in suppressing crystallization and achieving broadband optical absorption across both near-infrared (NIR) biological windows. Furthermore, direct experimental evidence demonstrating their effectiveness in broadband photothermal applications is scarce. To address these challenges, this study reports, for the first time, the synthesis of amorphous Pd-P-S quantum dots (a-Pd-P-S QDs) featuring engineered phosphorus-sulfur dual vacancies, fabricated via a facile laser ablation in liquid (LAL) method. This efficient physical technique effectively inhibits noble metal crystallization, enabling one-step production of Pd-based quantum dots with exceptional photothermal performance across the NIR-I (650-950 nm) and NIR-II (1000-1350 nm) spectral ranges. The synthesized quantum dots exhibit high photothermal conversion efficiency, excellent photothermal stability, and favorable biocompatibility. Photothermal heating and photothermal cytotoxicity were evaluated under both 808 nm (NIR-I) and 1064 nm (NIR-II) irradiation to substantiate the "Dual-NIR" capability, first in dispersion and then at the cellular level. While in vivo studies, 1064 nm laser was intentionally prioritized to leverage the practical advantages of the NIR-II window for deep-tissue applications. Notably, in vivo studies demonstrate that under 1064 nm laser irradiation at 1.0 W/cm2, the BSA/a-Pd-P-S QDs achieve a 91.8% suppression of tumor growth in a murine breast cancer model, with minimal systemic toxicity confirmed by hematological and histopathological analyses. This work not only introduces a universal and environmentally friendly laser-processing approach but also provides, for the first time, mechanistic insights into vacancy engineering within Pd-based quantum dots to enhance photothermal efficacy. These findings advance the development of next-generation deep-tissue theranostic platforms and expand the potential applications in future nanomedicine.
Developing efficient and durable oxygen evolution reaction (OER) electrocatalysts is essential for scalable hydrogen production via water splitting. While NiFe-layered double hydroxides (LDHs) are promising low-cost catalysts, their catalytic performance and stability remain limited. In this study, we report a one-step laser ablation in liquid (LAL) strategy to synthesize low-loading Ru-doped NiFe-LDH nanosheets (NiFeRu/C-LDH) with precisely controlled electronic and structural properties. The laser-driven uniform incorporation of Ru-4(+) into the NiFe-LDH lattice induces contraction and optimization of the local coordination environment. The resulting catalyst achieves low overpotentials of 236 and 299 mV at 10 and 100 mA cm(-)(2), respectively, in 1 M KOH, outperforming commercial IrO2 and undoped NiFe/C-LDH. It also demonstrates high durability with 95.3% activity retention after 200 h of continuous operation. Combined experimental and Density functional theory (DFT) calculations, the theoretical analyses reveal that strong Ru-O coordination and enhanced electronic interactions activate adjacent Fe sites, and establish a Fe-Ru dual active center configuration that facilitates OH- adsorption and lowers the energy barrier of the rate-determining O-O coupling step. This work offers a scalable laser-based synthesis route for high-performance electrocatalysts with tailored active sites.
The precise calibration of the electronic configuration of alloy catalysts to attain elevated electrocatalytic performance and industrial scalability is a formidable challenge. In this study, a universal laser ablation in liquid (LAL) strategy is developed for the implantation of interstitial hydrogen atoms into quaternary PdPtCuIn nanoalloys, resulting in a one-step, scalable formation of PdPtCuInHx nanoalloys. We reveal a "hydrogenmediated electronic modulation" mechanism, wherein hydrogen functions as a dynamic charge modulator. This process has been shown to induce localized electron redistribution, suppress elemental segregation in PdPtCuInHx nanoalloys, significantly improve size uniformity and crystalline state, activate Cu sites through charge transfer, and optimise the d-band centres of Pd and Pt. PdPtCuInHx nanoalloys demonstrate exceptional pH-universal HER performance, attributed to near-ideal hydrogen adsorption and accelerated water dissociation kinetics. It requires low overpotentials of only 187 mV@1000 mA cm- 2 in 0.5 M H2SO4 and 360 mV@1000 mA cm- 2 in 1.0 M KOH, surpassing commercial Pt/C and cutting-edge alloy catalysts. This catalyst displays no substantial degradation over a period of 1550 h of operation. Integrated into a proton exchange membrane water electrolyzer (PEMWE), it achieves 3 A cm- 2 at 1.9 V, with a voltage decay rate of 0.2 mV h- 1 over 600 h, meeting the U.S. DOE 2026 targets. This work offers a scalable route to metastable nanoalloys, and redefines the role of hydrogen as a design element for advanced electrocatalysts in sustainable energy conversion.
Purposely optimizing material structure to reduce the energy change of the rate‐determining step (RDS) for promoting oxygen evolution reaction (OER) catalytic performance is a major strategy to enhance the energy efficiency of electrocatalytic water splitting. Density functional theory (DFT) simulations indicate that creating a large number of defects on or inside the 2D FePS 3 is very beneficial for its catalytic reaction of OER, especially when there are more defects, the structural diversity of the surface is more conducive to the adsorption and reaction of intermediates. In particular, when Co‐doped FePS 3 surfaces produce a large number of S and P defects and expose metallic Fe as active sites, its catalytic performance, especially the catalytic stability, is significantly enhanced. A facile and efficient laser‐ablation‐in‐liquid method is then designed to combine Co with 2D layered crystal FePS 3 . Amazingly, the laser‐induced (Fe 0.53 Co 0.46 )PS 3 sample exhibits excellent OER performance, with an overpotential at 288 mV and a small Tafel slope of 58.3 mV dec −1 . Moreover, (Fe 0.53 Co 0.46 )PS 3 operates stably for 138 h at 10 mA cm −2 and 27 h at 100 mA cm −2 , which shows that the stability of (Fe 0.53 Co 0.46 )PS 3 far exceeds that of most of OER catalysts of Fe─Co system so far, and the comprehensive OER performance is in the first echelon of transition metal catalyst systems. This work proposes an in‐depth understanding of the structural mechanism design of massive phosphorus sulfur vacancies by laser‐induced manufacturing and will shed new light on promoting the stability of transition metal‐based OER catalysts without any precious alternatives.
Vertical few-layer graphene (VFLG) shows potential for application in electron sources, sensors and super- capacitors. However, the unclear nucleation mechanism still limits its controllable growth of VFLG with desired density and size. Herewith, the VFLG film with different size and density under different hydrogen plasma pretreatment time were synthesized and the individual VFLG shows good single-crystalline characterized by transmission electron microscopy. To make clear the mechanism of pretreatment time on the size and density of VFLG, the surface structure of silicon substrate before and after hydrogen plasma pretreatment were characterized by atomic force microscopy and wetting angle measurement. With the pretreatment time increases, the size of defects on the silicon substrate increased and quantities increased firstly and then decreased due to the competition of enlarging and fusion of themselves, which results in the size of the VFLG with cluster structure decreased firstly and then increased, while the density of the VFLG increased firstly and then decreased. The nucleation and growth process of VFLGs was observed by adjusting the growth time and the VFLG growth model was constructed which offers a new approach for controllable growth of VFLG. The discoveries not only shed light on the growth mechanism of VFLG, but also are beneficial for promoting the applications of VFLG.
Scalable water electrolysis requires mass-producible electrocatalysts for efficient hydrogen evolution reaction (HER) at high current densities. We developed a pulsed laser fusion method to synthesize Pd-CuInP2S6 composites on graphene or MXene Ti3C2 nanosheets. These catalysts exhibit enhanced charge transfer and abundant active sites, outperforming commercial Pt/C in both acidic (0.5 M H2SO4) and alkaline (1 M KOH) electrolytes. Density functional theory (DFT) analysis reveals synergistic HER enhancement via interstitial H and substituted In atoms. The optimized catalysts achieve remarkable overpotentials of -388 and -384 mV at 1,000 mA cm-2 (acid), with Tafel slopes of 61 and 67 mV dec-1, while demonstrating -455 and -450 mV overpotentials (alkaline) with 152 and 150 mV dec-1 Tafel slopes, respectively. They maintain exceptional stability over 10,000 CV cycles and extended operation at -500 mA cm-2, significantly surpassing Pt/C durability. This laser fabrication strategy enables scalable production of efficient, stable low-precious-metal catalysts for industrial HER.
The significant environmental challenges of dye‐contaminated wastewater necessitate efficient photocatalyst for pollutant degradation. Herein, a novel graphene quantum dots (GQDs) modified CuInP 2 S 6 composite (GQDs@CuInP 2 S 6 ) with a type‐II band alignment has been successfully synthesized via laser liquid phase melting technology. Under visible light, GQDs@CuInP 2 S 6 achieves 98.3% degradation of Rhodamine B (RhB) within 8 min, exhibiting a kinetic rate constant 2–3 orders of magnitude higher than pristine CuInP 2 S 6 . Density functional theory calculations reveal this enhancement stems from unique electronic modulation of CuInP 2 S 6 by GQDs. Notably, irrespective of van der Waals or covalent GQDs‐CuInP 2 S 6 interactions, the composite transitions from pristine CuInP 2 S 6 's a indirect bandgap to a direct bandgap, with chemisorbed GQDs further narrowing the gap, which facilitates electron transition and broadens light absorption spectrum. Additionally, the band alignment and partial charge density confirm a type‐II heterojunction in chemisorbed GQDs@CuInP 2 S 6 . Holes from GQDs@CuInP 2 S 6 and electrons from CuInP 2 S 6 generate an internal electric field, suppressing charge carrier recombination and significantly enhancing photocatalytic performance. This work pioneers a synthesis approach for quantum dot‐decorated surface composite and theoretically elucidates the quantum dot modification mechanisms, advancing a new innovative photocatalytic material design.
As a good carrier of hydrogen, ammonia-water has been employed to extract hydrogen in many ways. Here, we demonstrate a simple, green, ultrafast, and highly efficient method for hydrogen extraction from ammonia-water by laser bubbling in liquids (LBL) at room temperature and ambient pressure without catalyst. A maximum apparent yield of 33.7 mmol/h and a real yield of 93.6 mol/h were realized in a small operating space, which were far higher than the yields of most hydrogen evolution reactions from ammonia-water under ambient conditions. We also established that laser-induced cavitation bubbles generated a transient high temperature, which enabled a very suitable environment for hydrogen extraction from ammonia-water. The laser used here can serve as a demonstration of potentially solar-pumped catalyst-free hydrogen extraction and other chemical synthesis. We anticipate that the LBL technique will open unprecedented opportunities to produce chemicals.
Ultrafast N2 fixation reactions are quite challenging. Currently used methods for N2 fixation are limited, and strong dinitrogen bonds usually need to be activated via extreme temperature or pressure or by the use of an energy-consuming process with sophisticated catalysts. Herein, we report a novel laser-based chemical method for N2 fixation under ambient conditions without catalysts, this method is called laser bubbling in liquids (LBL), and it directly activates N2 in water (H2O) and efficiently converts N2 into valuable NH3 (max: 4.2 mmol h-1) and NO3- (0.17 mmol h-1). Remarkably, the highest yields of NH3 and NO3- are 4 orders of magnitude greater than the best values for electrocatalysis reported to date. Notably, we further validate the experimental mechanism by using optical emission spectroscopy to detect the production of intermediate plasma and by employing isotope tracing. We also establish that an extremely high-temperature environment far from thermodynamic equilibrium inside a laser-induced bubble and the kinetic process of rapid quenching of bubbles is crucial for N2 activation and fixation to generate NH3 and NOx via LBL. Based on these results, it is shown that LBL is a simple, safe, efficient, green, and sustainable technology that enables the rapid conversion of the renewable feedstocks H2O and N2 to NH3 and NO3-, facilitating new prospects for chemical N2 fixation.
Hydrogen (H 2 ) and hydrogen peroxide (H 2 O 2 ) play crucial roles as energy carriers and raw materials for industrial production. However, the current techniques for H 2 and H 2 O 2 production rely on complex catalysts and involve multiple intermediate steps. In this study, we present a straightforward, environmentally friendly, and highly efficient laser-induced conversion method for overall water splitting to simultaneously generate H 2 and H 2 O 2 at ambient conditions without any catalysts. The laser direct overall water splitting approach achieves an impressive light-to-hydrogen energy conversion efficiency of 2.1%, with H 2 production rates of 2.2 mmol/h and H 2 O 2 production rates of 65 µM/h in a limited reaction area (1 mm 2 ) within a short real reaction time (0.36 ms/h). Furthermore, we elucidate the underlying physics and chemistry behind the laser-induced water splitting to produce H 2 and H 2 O 2 . The laser-induced cavitation bubbles create an optimal microenvironment for water-splitting reactions because of the transient high temperatures (10 4 K) surpassing the chemical barrier required. Additionally, their rapid cooling rate (10 10 K/s) hinders reverse reactions and facilitates H 2 O 2 retention. Finally, upon bubble collapse, H 2 is released while H 2 O 2 remains dissolved in the water. Moreover, a preliminary amplification experiment demonstrates the potential industrial applications of this laser chemistry. These findings highlight that laser-based production of H 2 and H 2 O 2 from water holds promise as a straightforward, environmentally friendly, and efficient approach on an industrial scale beyond conventional chemical catalysis.
By combining Pd with 2D layered crystal CuInP2S6 (CIPS) via laser irradiation in liquids, low‐loading Pd@CIPS core–shell nanospheres are fabricated as an efficient and robust electrocatalysts for HER in both alkaline and acidic media under large current density (⩾1000 mA cm−2). Pd@CIPS core–shell nanosphere has two structural features, i) the out‐shell is the nanocomposite of PdHx and PdInHx, and ii) there is a kind of dendritic structure on the surface of nanospheres, while the dendritic structure porvides good gas desorption pathway and cause the Pd@CIPS system to maintain higher HER activity and stability than that of commercial Pt/C under large current densities. Pd@CIPS exhibits very low overpotentials of −218 and −313 mV for the large current density of 1000 mA cm−2, and has a small Tafel slope of 29 and 63 mV dec−1 in 0.5 m H2SO4 and 1 m KOH condition, respectively. Meanwhile, Pd@CIPS has an excellent stability under −10 and −500 mA cm−2 current densities and 50 000 cycles cyclic voltammetry tests in 0.5 m H2SO4 and 1 m KOH, respectively, which being much superior to that of commercial Pt/C. Density functional theory (DFT) reveals that engineering electronic structure of PdHx and PdInHx nanostructure can strongly weaken the Pd─H bonding.
Hydrogen (H2) and hydrogen peroxide (H2O2) play crucial roles as energy carriers and raw materials for industrial production. However, the current techniques for H2 and H2O2 production rely on complex catalysts and involve multiple intermediate steps. In this study, we present a straightforward, environmentally friendly, and highly efficient laser-induced conversion method for overall water splitting to simultaneously generate H2 and H2O2 at ambient conditions without any catalysts. The laser direct overall water splitting approach achieves an impressive light-to-hydrogen energy conversion efficiency of 2.1%, with H2 production rates of 2.2 mmol/h and H2O2 production rates of 65 µM/h in a limited reaction area (1 mm2) within a short real reaction time (0.36 ms/h). Furthermore, we elucidate the underlying physics and chemistry behind the laser-induced water splitting to produce H2 and H2O2. The laser-induced cavitation bubbles create an optimal microenvironment for water-splitting reactions because of the transient high temperatures (104 K) surpassing the chemical barrier required. Additionally, their rapid cooling rate (1010 K/s) hinders reverse reactions and facilitates H2O2 retention. Finally, upon bubble collapse, H2 is released while H2O2 remains dissolved in the water. Moreover, a preliminary amplification experiment demonstrates the potential industrial applications of this laser chemistry. These findings highlight that laser-based production of H2 and H2O2 from water holds promise as a straightforward, environmentally friendly, and efficient approach on an industrial scale beyond conventional chemical catalysis.
As emerging materials, medium-entropy oxides have attracted wide attention for the huge potential in energy storage, catalytic, magnetic and thermal applications. The electronic effect or the strong synergic effect caused by the construction of medium-entropy system leads to the unique properties of catalysis. In this contribution, we reported a medium-entropy CoNiCu oxide as an efficient cocatalyst for enhanced photocatalytic hydrogen evolution reaction. The target product was synthesized by a process of laser ablation in liquids and graphene oxide was applied as a conductive substrate of it, then it was loaded on the photocatalyst g-C3N4. The results showed that the modified photocatalysts exhibited the reduced Delta G(H)* and enhanced abilities of photoinduced charges separation and transfer. Furthermore, a maximum hydrogen production rate was measured to be 1177.52 mu mol center dot g(-1)center dot h(-1) under the visible light irradiation, which was about 291 times higher than that of pure gC3N4. These findings suggest that the medium-entropy CoNiCu oxide serves as an eminent cocatalyst, which offers a possible pathway towards the broadening of the applications of medium-entropy oxides and provides the alternatives to conventional cocatalysts.
Carbyne with one-dimensional sp-hybridized carbon atoms is the third form of carbon following diamond and graphite. Although carbyne nanocrystals have been synthesized, little is known about its structural details. Here, we report experimental evidence of the kinked structure of carbon chains and interchain van der Waals interaction of carbyne nanocrystals by near edge X-ray absorption fine structure (NEXAFS) spectroscopy. We measure the resonance and the feature peaks of the kinked configuration of carbon chains and the van der Waals interaction between chains of carbyne nanocrystals using NEXAFS spectroscopy. We also perform theoretical calculations of density functional theory and simulations based on the super-cell core-hole method for carbon K-edge NEXAFS. The theoretical results are in good agreement with the experimental measurements, which demonstrates that carbyne nanocrystals are van der Waals crystals with kinked chains as structural units. Note that the peak at 288.5 eV in the simulated NEXAFS spectrum implies the possible presence of hydrogen-terminated kinks or hydrogen-terminated chains in carbyne nanocrystals, which clarifies the understanding of the C-H bond in carbyne nanocrystals. These findings are enlightening and significant for pursuing physics and potential applications of carbyne.
Methanol (CH3OH) is a liquid hydrogen (H2) source that effectively releases H2 and is convenient for transportation. Traditional thermocatalytic CH3OH reforming reaction is used to produce H2, but this process needs to undergo high reaction temperature (e.g., 200 °C) along with a catalyst and a large amount of carbon dioxide (CO2) emission. Although photocatalysis and photothermal catalysis under mild conditions are proposed to replace the traditional thermal catalysis to produce H2 from CH3OH, they still inevitably produce CO2 emissions that are detrimental to carbon neutrality. Here, we, for the first time, report an ultrafast and highly selective production of H2 without any catalysts and no CO2 emission from CH3OH by laser bubbling in liquid (LBL) at room temperature and atmospheric pressure. We demonstrate that a super high H2 yield rate of 33.41 mmol·h-1 with 94.26% selectivity is achieved upon the laser-driven process. This yield is 3 orders of magnitude higher than the best value reported for photocatalytic and photothermal catalytic H2 production from CH3OH to date. The energy conversion efficiency of laser light to H2 and CO can be up to 8.5%. We also establish that the far from thermodynamic equilibrium state with high temperature inside the laser-induced bubble and the kinetic process of rapid quenching of bubbles play crucial roles in H2 production upon LBL. Thermodynamically, the high temperature induced using laser in bubbles ensures fast and efficient release of H2 from CH3OH decomposition. Kinetically, rapidly quenching of laser-induced bubbles can inhibit reverse reaction and can keep the products in the initial stage, which guarantees high selectivity. This study presents a laser-driven ultrafast and highly selective production of H2 from CH3OH under normal conditions beyond catalytic chemistry.
Hydrogen cyanide (HCN) is typically synthesized using ammonia and methane as sources of nitrogen and carbon, respectively, over expensive platinum catalysts at high temperatures. However, continuous high-temperature processing deactivates the catalyst, resulting in limited durability of the process. Besides, there are serious hazards and limitations in the further separation and utilization of HCN. From the perspective of sustainable synthesis and safe utilization, low-cost catalyst or catalyst-free synthesis, mild reaction conditions, and elimination of exposure to toxic reagents are becoming increasingly important. Direct synthesis of HCN from nitrogen (N2) at room temperature without any catalysts and its safe fixation into functional inorganic cyanides are desirable. Here, we report the catalyst-free synthesis of HCN by laser-induced activation of N2 and methanol (CH3OH) at room temperature and then the in situ synthesis of inorganic cyanides (silver and copper cyanides) without purification and separation by reacting the synthetic solution with noble metals. We also establish the possible reaction paths by density functional theory calculations and molecular dynamics simulations to elucidate the thermodynamics and kinetics of the reactions involved in the laser chemistry process, i.e., laser bubbling in liquid (LBL). The high temperature inside the laser-generated bubble overcomes the energy barrier and drives the successful coupling of carbon and nitrogen sources endergonically in the following process. Bubbles experience a rapid quench during the LBL process, resulting in the kinetic control product HCN with high efficiency. The method is viable for the catalyst-free direct synthesis of HCN from N2 and CH3OH at normal conditions for safe fixation into inorganic cyanides.
One promising way to tune the physicochemical properties of materials and optimize their performance in various potential applications is to engineer material structures at the atomic level. As is well known, the performance of Pd-based catalysts has long been constrained by surface contamination and their single structure. Here, we employed an unadulterated top-down synthesis method, known as laser fragmentation in liquid (LFL), to modify pristine PdPS crystals and obtained a kind of metastable palladium-sulfur compound nanoparticles (LFL-PdS NPs) as a highly efficient electrocatalyst for hydrogen evolution reaction (HER). Laser fragmentation of the layered PdPS crystal led to a structural reorganization at the atomic level and resulted in the formation of uniform metastable LFL-PdS NPs. Noteworthy, the LFL-PdS NPs show excellent electrocatalytic HER performance and stability in acidic media, with an overpotential of –66 mV at 10 mA⋅cm−2, the Tafel slope of 42 mV⋅dec−1. The combined catalytic performances of our LFL-PdS NPs are comparable to the Pt/C catalyst for HER. This work provides a top-down synthesis strategy as a promising approach to design highly active metastable metal composite electrocatalysts for sustainable energy applications.
Carbon dioxide (CO2) reduction is a possible way to solve the green-house effect. Conventional catalytic CO2 reduction faces some problems, such as high free energy barriers, limitation of cheap and effective catalysts. Here, we develop a highly efficient and high-ly selective CO2 reduction under mild conditions by laser reduction in liquid (LRL). A high CO yield of 12.3 mmol h-1 with near 100% selectivity and 13.3% energy conversion efficiency of laser to CO is achieved. In LRL, abundant active species are created immediately by laser-induced plasma in small bubbles along with transient extremely high temperature. Thermodynamically, CO2 reduction proceeds quickly with the interaction of active species at high tem-perature. Kinetically, the rapid quenching process inhibits reverse reaction and keeps products at initial stage. The synergy of thermo-dynamics and kinetics results in high yield and high selectivity. These findings provide an alternative approach for CO2 reduction under ambient conditions.
An interface between amorphous and crystalline phases plays an important role in improving the photocatalytic performance due to the optimization of both the conductivity and the reaction activity of active sites of cocatalysts simultaneously.