Ultralow Catalytic Loading for Optimised Electrocatalytic Performance of AuPt Nanoparticles to Produce Hydrogen and Ammonia.

The hydrogen evolution and nitrite reduction reactions are key to producing green hydrogen and ammonia. Antenna-reactor nanoparticles hold promise to improve the performances of these transformations under visible-light excitation, by combining plasmonic and catalytic materials. However, current materials involve compromising either on the catalytic activity or the plasmonic enhancement and also lack control of reaction selectivity. Here, we demonstrate that ultralow loadings and non-uniform surface segregation of the catalytic component optimize catalytic activity and selectivity under visible-light irradiation. Taking Pt-Au as an example we find that fine-tuning the Pt content produces a 6-fold increase in the hydrogen evolution compared to commercial Pt/C as well as a 6.5-fold increase in the nitrite reduction and a 2.5-fold increase in the selectivity for producing ammonia under visible light excitation relative to dark conditions. Density functional theory suggests that the catalytic reactions are accelerated by the intimate contact between nanoscale Pt-rich and Au-rich regions at the surface, which facilitates the formation of electron-rich hot-carrier puddles associated with the Pt-based active sites. The results provide exciting opportunities to design new materials with improved photocatalytic performance for sustainable energy applications.

Triple Play of Band Gap, Interband, and Plasmonic Excitations for Enhanced Catalytic Activity in Pd/HxMoO3 Nanoparticles in the Visible Region.

Plasmonic photocatalysis has been limited by the high cost and scalability of plasmonic materials, such as Ag and Au. By focusing on earth-abundant photocatalyst/plasmonic materials (HxMoO3) and Pd as a catalyst, we addressed these challenges by developing a solventless mechanochemical synthesis of Pd/HxMoO3 and optimizing photocatalytic activities in the visible range. We investigated the effect of HxMoO3 band gap excitation (at 427 nm), Pd interband transitions (at 427 nm), and HxMoO3 localized surface plasmon resonance (LSPR) excitation (at 640 nm) over photocatalytic activities toward the hydrogen evolution and phenylacetylene hydrogenation as model reactions. Although both excitation wavelengths led to comparable photoenhancements, a 110% increase was achieved under dual excitation conditions (427 + 640 nm). This was assigned to a synergistic effect of optical excitations that optimized the generation of energetic electrons at the catalytic sites. These results are important for the development of visible-light photocatalysts based on earth-abundant components.

Enhancing Oxygen Evolution Reaction Performance in Prussian Blue Analogues: Triple-Play of Metal Exsolution, Hollow Interiors, and Anionic Regulation.

Prussian blue analogs (PBAs) are promising catalysts for green hydrogen production. However, the rational design of high-performing PBAs is challenging, which requires an in-depth understanding of the catalytic mechanism. Here FeMn@CoNi core-shell PBAs are employed as precursors, together with Se powders, in low-temperature pyrolysis in an argon atmosphere. This synthesis method enables the partial dissociation of inner FeMn PBAs that results in hollow interiors, Ni nanoparticles (NPs) exsolution to the surface, and Se incorporation onto the PBA shell. The resulting material presents ultralow oxygen evolution reaction (OER) overpotential (184 mV at 10 mA cm-2 ) and low Tafel slope (43.4 mV dec-1 ), outperforming leading-edge PBA-based electrocatalysts. The mechanism responsible for such a high OER activity is revealed, assisted by density functional theory (DFT) calculations and the surface examination before and after the OER process. The exsolved Ni NPs are found to help turn the PBAs into Se-doped core-shell metal oxyhydroxides during the OER, in which the heterojunction with Ni and the Se incorporation are combined to improve the OER kinetics. This work shows that efficient OER catalysts could be developed by using a novel synthesis method backed up by a sound understanding and control of the catalytic pathway.

Controlling Selectivity in Plasmonic Catalysis: Switching Reaction Pathway from Hydrogenation to Homocoupling Under Visible-Light Irradiation.

Plasmonic catalysis enables the use of light to accelerate molecular transformations. Its application to the control reaction selectivity is highly attractive but remains challenging. Here, we have found that the plasmonic properties in AgPd nanoparticles allowed different reaction pathways for tunable product formation under visible-light irradiation. By employing the hydrogenation of phenylacetylene as a model transformation, we demonstrate that visible-light irradiation can be employed to steer the reaction pathway from hydrogenation to homocoupling. Our data showed that the decrease in the concentration of H species at the surface due to plasmon-enhanced H2 desorption led to the control in selectivity. These results provide important insights into the understanding of reaction selectivity with light, paving the way for the application of plasmonic catalysis to the synthesis of 1,3-diynes, and bringing the vision of light-driven transformations with target selectivity one step closer to reality.

Highly Efficient and Selective Photocatalytic Nonoxidative Coupling of Methane to Ethylene over Pd-Zn Synergistic Catalytic Sites.

Photocatalytic nonoxidative coupling of CH4 to multicarbon (C2+) hydrocarbons (e.g., C2H4) and H2 under ambient conditions provides a promising energy-conserving approach for utilization of carbon resource. However, as the methyl intermediates prefer to undergo self-coupling to produce ethane, it is a challenging task to control the selective conversion of CH4 to higher value-added C2H4. Herein, we adopt a synergistic catalysis strategy by integrating Pd-Zn active sites on visible light-responsive defective WO3 nanosheets for synergizing the adsorption, activation, and dehydrogenation processes in CH4 to C2H4 conversion. Benefiting from the synergy, our model catalyst achieves a remarkable C2+ compounds yield of 31.85 µmol·g-1·h-1 with an exceptionally high C2H4 selectivity of 75.3% and a stoichiometric H2 evolution. In situ spectroscopic studies reveal that the Zn sites promote the adsorption and activation of CH4 molecules to generate methyl and methoxy intermediates with the assistance of lattice oxygen, while the Pd sites facilitate the dehydrogenation of methoxy to methylene radicals for producing C2H4 and suppress overoxidation. This work demonstrates a strategy for designing efficient photocatalysts toward selective coupling of CH4 to higher value-added chemicals and highlights the importance of synergistic active sites to the synergy of key steps in catalytic reactions.

Achieving enhanced peroxidase-like activity in multimetallic nanorattles.

Gold nanoparticles (Au NPs) have been extensively used as artificial enzymes, but their performance is still limited. We address this challenge by focusing on multimetallic nanorattles comprising an Au core inside a bimetallic AgAu shell, separated by a void (Au@AgAu NRs). They were prepared by a galvanic replacement approach and contained an ultrathin and porous shell comprising an AgAu alloy. By investigating the peroxide-like activity using TMB oxidation as a model transformation, we have found an increase of 152 fold in activities for the NRs relative to conventional Au NPs. Based on the kinetics results, the NRs also showed the lowest Km, indicating better interaction with the substrate and faster product formation. We also observed a linear relationship between the concentration of the product and oxTMB as a function of H2O2 concentration, which could be further applied for H2O2 sensing applications (colorimetric detection). These data suggest that the NRs enable the combined effect of an increased surface area relative to solid counterparts, the possibility of exposing highly active surface sites, and the exploitation of nanoconfinement effects due to the void regions between the core and shell components. These results provide important insights into the optimization of peroxidase-like performances beyond what can be achieved in conventional NPs and may inspire the development of better-performing artificial enzymes.

Plasmonic catalysis with designer nanoparticles.

Catalysis is central to a more sustainable future and a circular economy. If the energy required to drive catalytic processes could be harvested directly from sunlight, the possibility of replacing contemporary processes based on terrestrial fuels by the conversion of light into chemical energy could become a step closer to reality. Plasmonic catalysis is currently at the forefront of photocatalysis, enabling one to overcome the limitations of "classical" wide bandgap semiconductors for solar-driven chemistry. Plasmonic catalysis enables the acceleration and control of a variety of molecular transformations due to the localized surface plasmon resonance (LSPR) excitation. Studies in this area have often focused on the fundamental understanding of plasmonic catalysis and the demonstration of plasmonic catalytic activities towards different reactions. In this feature article, we discuss recent contributions from our group in this field by employing plasmonic nanoparticles (NPs) with controllable features as model systems to gain insights into structure-performance relationships in plasmonic catalysis. We start by discussing the effect of size, shape, and composition in plasmonic NPs over their activities towards LSPR-mediated molecular transformations. Then, we focus on the effect of metal support interactions over activities, reaction selectivity, and reaction pathways. Next, we shift to the control over the structure in hollow NPs and nanorattles. Inspired by the findings from these model systems, we demonstrate a design-driven strategy for the development of plasmonic catalysts based on plasmonic-catalytic multicomponent NPs for two types of molecular transformations: the selective hydrogenation of phenylacetylene and the oxygen evolution reaction. Finally, future directions, challenges, and perspectives in the field of plasmonic catalysis with designer NPs are discussed. We believe that the examples and concepts presented herein may inspire work and progress in plasmonic catalysis encompassing the design of plasmonic multicomponent materials, new strategies to control reaction selectivity, and the unraveling of stability and reaction mechanisms.

Recent Advances in Plasmonic Photocatalysis Based on TiO2 and Noble Metal Nanoparticles for Energy Conversion, Environmental Remediation, and Organic Synthesis.

Plasmonic photocatalysis has emerged as a prominent and growing field. It enables the efficient use of sunlight as an abundant and renewable energy source to drive a myriad of chemical reactions. For instance, plasmonic photocatalysis in materials comprising TiO2 and plasmonic nanoparticles (NPs) enables effective charge carrier separation and the tuning of optical response to longer wavelength regions (visible and near infrared). In fact, TiO2 -based materials and plasmonic effects are at the forefront of heterogeneous photocatalysis, having applications in energy conversion, production of liquid fuels, wastewater treatment, nitrogen fixation, and organic synthesis. This review aims to comprehensively summarize the fundamentals and to provide the guidelines for future work in the field of TiO2 -based plasmonic photocatalysis comprising the above-mentioned applications. The concepts and state-of-the-art description of important parameters including the formation of Schottky junctions, hot electron generation and transfer, near field electromagnetic enhancement, plasmon resonance energy transfer, scattering, and photothermal heating effects have been covered in this review. Synthetic approaches and the effect of various physicochemical parameters in plasmon-mediated TiO2 -based materials on performances are discussed. It is envisioned that this review may inspire and provide insights into the rational development of the next generation of TiO2 -based plasmonic photocatalysts with target performances and enhanced selectivities.

Localized Orbital Excitation Drives Bond Formation in Plasmonic Catalysis.

Localized surface plasmons generated on metallic nanostructures can be used to accelerate molecular transformations; however, the efficiency is limited by the challenge to control the energy/charge transfer at the interfaces. Here, we combine density functional theory (DFT) calculations and experiments to reveal the mechanism of nitrophenol reduction on Au nanoparticles under visible-light irradiation and propose a strategy to further enhance the reaction rates. DFT calculations show a reduced activation barrier under electronic excitation on Au(111), thus explaining the measured higher rates under visible-light irradiation. Furthermore, we propose a heterostructure with Au nanoparticles covered by a thin film of hexagonal boron nitride; the latter is used to decouple the molecular orbitals from the metal to enable charge localization in the molecule. DFT calculations show that by this electronic decoupling, the activation barrier can be lowered by a factor of five. This work thus provides a valuable strategy for optimizing catalytic efficiency in plasmonic photocatalysis.

A photoelectrochemical enzyme biosensor based on functionalized hematite microcubes for rutin determination by square-wave voltammetry.

A photoelectrochemical biosensing strategy for the highly sensitive detection of the flavonoid rutin was developed by synergizing the photoelectrocatalytic properties of hematite (α-Fe2O3) decorated with palladium nanoparticles (PdNPs) and the biocatalysis towards laccase-based reactions. The integration of α-Fe2O3.PdNPs with a polyphenol oxidase as a biorecognition element yields a novel biosensing platform. Under visible light irradiation, the photoactive biocomposite can generate a stable photocurrent, which was found to be directly dependent upon the concentration of rutin. Under the optimal experimental conditions, the cathodic photocurrent, measured at 0.33 V vs. Ag/AgCl, from the square-wave voltammograms presented a linear dependence on the rutin concentration within the range of 0.008-30.0 × 10-8 mol L-1 (sensitivity: 1.7 µA·(× 10-8 M-1)·cm-2), with an experimental detection limit (S/N = 3) of 8.4 × 10-11 mol L-1. The proposed biosensor device presented good selectivity towards rutin in the presence of various organic compounds and inorganic ions, demonstrating the potential application of this biosensing platform in complex matrices. This bioanalytical device also exhibited excellent operational and analytical properties, such as intra-day (standard deviation, SD = 0.21%) and inter-day (SD = 1.30%) repeatability, and long storage stability (SD = 2.80% over 30 days).Graphical abstract.

Enhanced Spontaneous Antibacterial Activity of δ-MnO2 by Alkali Metals Doping.

Recently, the widespread use of antibiotics is becoming a serious worldwide public health challenge, which causes antimicrobial resistance and the occurrence of superbugs. In this context, MnO2 has been proposed as an alternative approach to achieve target antibacterial properties on Streptococcus mutans (S. mutans). This requires a further understanding on how to control and optimize antibacterial properties in these systems. We address this challenge by synthesizing δ-MnO2 nanoflowers doped by magnesium (Mg), sodium (Na), and potassium (K) ions, thus displaying different bandgaps, to evaluate the effect of doping on the bacterial viability of S. mutans. All these samples demonstrated antibacterial activity from the spontaneous generation of reactive oxygen species (ROS) without external illumination, where doped MnO2 can provide free electrons to induce the production of ROS, resulting in the antibacterial activity. Furthermore, it was observed that δ-MnO2 with narrower bandgap displayed a superior ability to inhibit bacteria. The enhancement is mainly attributed to the higher doping levels, which provided more free electrons to generate ROS for antibacterial effects. Moreover, we found that δ-MnO2 was attractive for in vivo applications, because it could nearly be degraded into Mn ions completely following the gradual addition of vitamin C. We believe that our results may provide meaningful insights for the design of inorganic antibacterial nanomaterials.

Automated Single-Particle Reconstruction of Heterogeneous Inorganic Nanoparticles.

Single-particle reconstruction can be used to perform three-dimensional (3D) imaging of homogeneous populations of nano-sized objects, in particular viruses and proteins. Here, it is demonstrated that it can also be used to obtain 3D reconstructions of heterogeneous populations of inorganic nanoparticles. An automated acquisition scheme in a scanning transmission electron microscope is used to collect images of thousands of nanoparticles. Particle images are subsequently semi-automatically clustered in terms of their properties and separate 3D reconstructions are performed from selected particle image clusters. The result is a 3D dataset that is representative of the full population. The study demonstrates a methodology that allows 3D imaging and analysis of inorganic nanoparticles in a fully automated manner that is truly representative of large particle populations.

Preparation of Silver-Palladium Alloyed Nanoparticles for Plasmonic Catalysis under Visible-Light Illumination.

Localized surface plasmon resonance (LSPR) in plasmonic nanoparticles (NPs) can accelerate and control the selectivity of a variety of molecular transformations. This opens possibilities for the use of visible or near-IR light as a sustainable input to drive and control reactions when plasmonic nanoparticles supporting LSPR excitation in these ranges are employed as catalysts. Unfortunately, this is not the case for several catalytic metals such as palladium (Pd). One strategy to overcome this limitation is to employ bimetallic NPs containing plasmonic and catalytic metals. In this case, the LSPR excitation in the plasmonic metal can contribute to accelerate and control transformations driven by the catalytic component. The method reported herein focuses on the synthesis of bimetallic silver-palladium (Ag-Pd) NPs supported on ZrO2 (Ag-Pd/ZrO2) that acts as a plasmonic-catalytic system. The NPs were prepared by co-impregnation of corresponding metal precursors on the ZrO2 support followed by simultaneous reduction leading to the formation of bimetallic NPs directly on the ZrO2 support. The Ag-Pd/ZrO2 NPs were then used as plasmonic catalysts for the reduction of nitrobenzene under 425 nm illumination by LED lamps. Using gas chromatography (GC), the conversion and selectivity of the reduction reaction under the dark and light irradiation conditions can be monitored, demonstrating the enhanced catalytic performance and control over selectivity under LSPR excitation after alloying non-plasmonic Pd with plasmonic metal Ag. This technique can be adapted to a wide range of molecular transformations and NPs compositions, making it useful for the characterization of the plasmonic catalytic activity of different types of catalysis in terms of conversion and selectivity.

Tandem X-ray absorption spectroscopy and scattering for in situ time-resolved monitoring of gold nanoparticle mechanosynthesis.

Current time-resolved in situ approaches limit the scope of mechanochemical investigations possible. Here we develop a new, general approach to simultaneously follow the evolution of bulk atomic and electronic structure during a mechanochemical synthesis. This is achieved by coupling two complementary synchrotron-based X-ray methods: X-ray absorption spectroscopy (XAS) and X-ray diffraction. We apply this method to investigate the bottom-up mechanosynthesis of technologically important Au micro and nanoparticles in the presence of three different reducing agents, hydroquinone, sodium citrate, and NaBH4. Moreover, we show how XAS offers new insight into the early stage generation of growth species (e.g. monomers and clusters), which lead to the subsequent formation of nanoparticles. These processes are beyond the detection capabilities of diffraction methods. This combined X-ray approach paves the way to new directions in mechanochemical research of advanced electronic materials.

Hot Electrons, Hot Holes, or Both? Tandem Synthesis of Imines Driven by the Plasmonic Excitation in Au/CeO2 Nanorods.

Solar-to-chemical conversion via photocatalysis is of paramount importance for a sustainable future. Thus, investigating the synergistic effects promoted by light in photocatalytic reactions is crucial. The tandem oxidative coupling of alcohols and amines is an attractive route to synthesize imines. Here, we unravel the performance and underlying reaction pathway in the visible-light-driven tandem oxidative coupling of benzyl alcohol and aniline employing Au/CeO2 nanorods as catalysts. We propose an alternative reaction pathway for this transformation that leads to improved efficiencies relative to individual CeO2 nanorods, in which the localized surface plasmon resonance (LSPR) excitation in Au nanoparticles (NPs) plays an important role. Our data suggests a synergism between the hot electrons and holes generated from the LSPR excitation in Au NPs. While the oxygen vacancies in CeO2 nanorods trap the hot electrons and facilitate their transfer to adsorbed O2 at surface vacancy sites, the hot holes in the Au NPs facilitate the α-H abstraction from the adsorbed benzyl alcohol, evolving into benzaldehyde, which then couples with aniline in the next step to yield the corresponding imine. Finally, cerium-coordinated superoxide species abstract hydrogen from the Au surface, regenerating the catalyst surface.

Visible light plasmon excitation of silver nanoparticles against antibiotic-resistant Pseudomonas aeruginosa.

The interaction of metallic nanoparticles with light excites a local surface plasmon resonance (LSPR). This phenomenon enables the transfer of hot electrons to substrates that release Reactive Oxygen Species (ROS). In this context, the present study aimed at enhancing the antibacterial effect of citrate-covered silver nanoparticles (AgNPs) by LSPR excitation with visible LED. AgNPs possess excellent antimicrobial properties against Pseudomonas aeruginosa, one of the most refractory organisms to antibiotic treatment. The Minimum Inhibitory Concentration (MIC) of the AgNPs was 10 µg/ml under dark conditions and 5 µg/ml under light conditions. The combination of light and AgNPs led to 100% cell death after 60 min. Flow cytometry quantification showed that bacteria treated with LSPR-stimulated AgNPs displayed 4.8 times more ROS. This significant increase in ROS possibly accounts for most of the antimicrobial effect of the AgNPs. In addition, light exposition caused a small release of silver ions (0.4%) suggesting that silver ions may play a secondary role in P. aeruginosa death. Overall, the results presented here show that LSPR stimulation of AgNPs by visible light enhances the antimicrobial activity of silver nanoparticles and can be an alternative for the treatment of topic infections caused by antibiotic-resistant bacteria such as P. aeruginosa.

Design-controlled synthesis of IrO2 sub-monolayers on Au nanoflowers: marrying plasmonic and electrocatalytic properties.

We develop herein plasmonic-catalytic Au-IrO2 nanostructures with a morphology optimized for efficient light harvesting and catalytic surface area; the nanoparticles have a nanoflower morphology, with closely spaced Au branches all partially covered by an ultrathin (1 nm) IrO2 shell. This nanoparticle architecture optimizes optical features due to the interactions of closely spaced plasmonic branches forming electromagnetic hot spots, and the ultra-thin IrO2 layer maximizes efficient use of this expensive catalyst. This concept was evaluated towards the enhancement of the electrocatalytic performances towards the oxygen evolution reaction (OER) as a model transformation. The OER can play a central role in meeting future energy demands but the performance of conventional electrocatalysts in this reaction is limited by the sluggish OER kinetics. We demonstrate an improvement of the OER performance for one of the most active OER catalysts, IrO2, by harvesting plasmonic effects from visible light illumination in multimetallic nanoparticles. We find that the OER activity for the Au-IrO2 nanoflowers can be improved under LSPR excitation, matching best properties reported in the literature. Our simulations and electrocatalytic data demonstrate that the enhancement in OER activities can be attributed to an electronic interaction between Au and IrO2 and to the activation of Ir-O bonds by LSPR excited hot holes, leading to a change in the reaction mechanism (rate-determinant step) under visible light illumination.

Chemometric-assisted construction of a biosensing device to measure chlorogenic acid content in brewed coffee beverages to discriminate quality.

In this work we propose the use of statistical mixture design in the construction of a biosensor device based on graphite oxide, platinum nanoparticles and biomaterials obtained from Botryosphaeria rhodina MAMB-05. The biosensor was characterized by electrochemical impedance spectroscopy. Under optimized experimental parameters by factorial design, the biosensor was applied to the voltammetric determination of chlorogenic acid (CGA) measured as 5-O-caffeoylquinic acid (5-CQA). The biosensor response was linear (R2 = 0.998) for 5-CQA in the concentration range 0.56-7.3 µmol L-1, with limit of detection and quantification of 0.18 and 0.59 µmol L-1, respectively. The new biosensing device was applied to quality control analysis based upon the determination of CGA content in specialty and traditional coffee beverages. The results indicated that specialty coffee had a significantly higher content of CGA. Principal component analysis of the voltammetric fingerprint of brewed coffees revealed that the laccase-based biosensor can be used for their discrimination.

Synthesis, Transformation, and Utilization of Monodispersed Colloidal Spheres.

Colloidal particles with a spherical shape and diameters in the range of 0.01-1 µm have been a subject of extensive research, with applications in areas such as photonics, electronics, catalysis, drug delivery, and medicine. For most of these applications, it is of critical importance to achieve monodispersity for the size while expanding the diversity in terms of structure and composition. The uniformity in size allows one to establish rigorous correlations between this parameter and the physicochemical properties of the colloidal particles while ensuring experimental repeatability and measurement accuracy. On the other hand, the diversity in structure and composition offers additional handles for tailoring the properties. By switching from the conventional plain, solid structure to a core-shell, hollow, porous, or Janus structure, it offers immediate advantages and creates new opportunities, especially in the context of self-assembly, encapsulation, and controlled release. As for composition, monodispersed colloidal spheres were traditionally limited to amorphous materials such as polystyrene and silica. For metals and semiconducting materials, which are more valuable to applications in photonics, electronics, and catalysis, they tend to crystallize and thus grow anisotropically into nonspherical shapes, especially when their sizes pass 0.1 µm. Taken together, it is no wonder why chemical synthesis of monodispersed colloidal spheres has been a constant theme of research in areas such as colloidal science, materials chemistry, materials science, and soft matter. In this Account, we summarize our efforts over the past two decades in developing solution-phase methods for the facile synthesis of colloidal spheres that are uniform in size, together with a broad range of compositions (including metals and semiconductors) and structures (e.g., solid, core-shell, hollow, porous, and Janus, among others). We start with the synthesis of monodispersed colloidal spheres made of semiconductors, metals with low melting points, and precious metals. Through chemical reactions, these colloidal spheres can be transformed into core-shell or hollow structures with new compositions and properties. Next, we discuss the synthesis of colloidal spheres with a Janus structure while taking a pseudospherical shape. Specifically, metal-polymer hybrid particles composed of one metal nanoparticle partially embedded in the surface of a polymer sphere can be produced through precipitation polymerization in the presence of metal seed. With these Janus particles serving as templates, other types of Janus structures such as hollow spheres with a single hole in the surface can be obtained via site-selected deposition. Alternatively, such hollow spheres can be fabricated through a physical transformation process that involves swelling of polymer spheres, followed by freeze-drying. All these synthesis and transformation processes are solution-based, offering flexibility and potential for large-scale production. At the end, we highlight some of the applications enabled by these colloidal spheres, including fabrication of photonic devices, encapsulation, and controlled release for nanomedicine.

Investigating the repair of alveolar bone defects by gelatin methacrylate hydrogels-encapsulated human periodontal ligament stem cells.

Although various efforts have been made to develop effective treatments for alveolar bone defect, alveolar regeneration has been emerging as the one with the most potential Herein, we investigated the potential of gelatin methacrylate (GelMA) hydrogels-encapsulated human periodontal ligament stem cells (hPDLSCs) to regenerate alveolar bone. The easy, rapid, and cost-effective nature of GelMA hydrogels makes them a promising mode of stem cell-delivery for clinically relevant alveolar bone regeneration. More importantly, GelMA hydrogels provide an optimal niche for hPDLSCs proliferation, migration and osteogenic differentiation, which are critical for alveolar bone regeneration. In this study, we examined the microstructure of GelMA hydrogels, and identified a highly porous and interconnected network. Compressive test of GelMA hydrogels showed that the stress reached a maximum value of 13.67 ± 0.03 kPa when the strain reached 55%. The maximum values of swelling ratio were 700 ± 47% at the fifth hour. The proliferation rate of hPDLSCs in the GelMA hydrogels resembled that in 2D culture and gradually increased. We established a critical-sized rat model of alveolar bone defects, and applied Micro-CT to assess new bone formation. Compared to the control group, there was substantial bone regeneration in the GelMA + hPDLSCs group at both 4 and 8 weeks after the operation. Histological analysis results were consistent with Micro-CT results. Our study demonstrates that the GelMA hydrogels-encapsulated hPDLSCs have a significant alveolar regenerative potential, and may represent a new strategy for the therapy of alveolar bone defects.