High-Rate Nonaqueous Mg-CO2 Batteries Enabled by Mo2 C-Nanodot-Embedded Carbon Nanofibers.

The widespread acceptance of nonaqueous rechargeable metal-gas batteries, known for their remarkably high theoretical energy density, faces obstacles such as poor reversibility and low energy efficiency under high charge-discharge current densities. To tackle these challenges, a novel catalytic cathode architecture for Mg-CO2 batteries, fabricated using a one-pot electrospinning method followed by heat treatment, is presented. The resulting structure features well-dispersed molybdenum carbide nanodots embedded within interconnected carbon nanofibers, forming a 3D macroporous conducting network. This cathode design enhances the volumetric efficiency, enabling effective discharge product deposition, while also improving electrical properties and boosting catalytic activity. This enhancement results in high discharge capacities and excellent rate capabilities, while simultaneously minimizing voltage hysteresis and maximizing energy efficiency. The battery exhibits a stable cycle life of over 250 h at a current density of 200 mA g-1 with a low initial charge-discharge voltage gap of 0.72 V. Even at incredibly high current densities, reaching 1600 mA g-1 , the battery maintains exceptional performance. These findings highlight the crucial role of cathode architecture design in enhancing the performance of Mg-CO2 batteries and hold promise for improving other metal-gas batteries that involve deposition-decomposition reactions.

Self-Zincophilic Dual Protection Host of 3D ZnO/Zn⊂CF to Enhance Zn Anode Cyclability.

Zn dendrite growth and side reactions restrict the practical use of Zn anode. Herein, the design of a novel 3D hierarchical structure is demonstrated with self-zincophilic dual-protection constructed by ZnO and Zn nanoparticles immobilized on carbon fibers (ZnO/Zn⊂CF) as a versatile host on the Zn surface. The unique 3D frameworks with abundant zinc nucleation storage sites can alleviate the structural stress during the plating/stripping process and overpower Zn dendrite growth by moderating Zn2+ flux. Moreover, given the dual protection design, it can reduce the contact area between active zinc and electrolyte, inhibiting hydrogen evolution reactions. Importantly, density functional theory calculations and experimental results confirm that the introduced O atoms in ZnO/Zn⊂CF enhance the interaction between Zn2+ and the host and reduce Zn nucleation overpotential. As expected, the ZnO/Zn⊂CF-Zn electrode exhibits stable Zn plating/stripping with low polarization for 4200 h at 0.2 mA cm-2 and 0.2 mAh cm-2. Furthermore, the symmetrical cell displays a significantly long cycling life of over 1800 h, even at 30 mA cm-2. The fabricated full cells also show impressive cycling performance when coupled with V2O3 cathodes.

Ti3C2Tx MXene as Intriguing Material for Electrochemical Capacitor.

This study provides meaningful insight into the charge storage in Ti3C2Tx MXene (M-transition metal, X-carbon, T-Cl, F, O) for electrochemical capacitor (EC) application. The experiments show that this 2D material is especially adapted for the hydrogen electrosorption under negative polarization. It is found that hydrogen bonding to the Ti3C2Tx surface occurs through interactions of various strength. Different mechanisms are suggested to explain the nature of H stored at the electrode/electrolyte interface depending on pH and potential range. For the negative potentials, both capacitive and faradaic currents are involved, and the electrode can operate in a relatively wide range. On the other hand, the narrow range of positive potentials limits whole voltage of EC. Such charge disproportion has a major impact on the performance failure of symmetric MXene-based ECs. New design of MXene cells with a wide operating voltage is introduced. To equalize the charge storage of both electrodes, the positive Ti3C2Tx electrode is replaced by the porous carbon (BP2000) with a wide working potential and a good capacitive response. Thus, EC operating voltage is considerably expanded to 1.3, 1.4, 2 V in acidic, basic, neutral medium, respectively. During cycling tests at 1 A g-1, the asymmetric cell MXene/BP2000 maintains 80% of initial capacitance after 22 000 cycles.

α-Bi2Mo3O12: A Dual-Functional material for electrocatalytic water splitting and supercapacitor applications.

This study explores the functionality of α-Bi2Mo3O12 (BMO) as an electrocatalyst for water splitting and its suitability for supercapacitor applications. BMO was synthesized by the solvothermal method and characterized in pre-calcination [BMO (BC)], post-calcination [BMO (AC)], and base-etched forms [BMO (BE)]. Structural analysis confirmed the formation of α-Bi2Mo3O12 with well-defined crystallographic planes. Electrochemical analysis revealed that BMO (AC) exhibited the lowest overpotential for hydrogen evolution reactions (HER) and BMO (BC) exhibited the lowest overpotential for oxygen evolution reactions (OER), indicating its superior electrocatalytic activity. The Tafel slope and electrochemical impedance spectroscopy results confirmed the superior kinetics and charge transfer properties of BMO material. Furthermore, BMO samples demonstrated excellent stability during prolonged chronoamperometry (CA) testing for 12 h. For supercapacitor performances, the BMO (BE) exhibits a superior specific capacitance value of 398 F/g at 2.0 A/g. Thus, the BMO material delivers prominent electrocatalytic activity as well as supercapacitor performance. Overall, this study demonstrates the potentiality of α-Bi2Mo3O12 in different forms as a dual-functional material for efficient energy storage and conversion.

Selecting non-metal doped FeS2 as efficient sulfur cathode host for enhanced Li-S redox chemistry.

Lithium-sulfur batteries (LSBs) are considered as the development direction of the new generation energy storage system due to their high energy density and low cost. The slow redox kinetics of sulfur and the shuttle effect of lithium polysulfide (LiPS) are considered to be the main obstacles to the practical application of LSBs. Transition-metal sulfide as the cathode host can improve the Li-S redox chemistry. However, there has been no investigation of the application of FeS2 host in Li-S redox chemistry. Applying the first-principles calculations, we investigated the formation energy, band gap, Li+ diffusion, adsorption energy, catalytic performance and Li2 S decomposition barrier of FeAx S2-x (A=N, P, O, Se; x=0, 0.125, 0.25, 0.375) to explore the Li-S redox chemistry and finally select excellent host material. FeA0.25 S1.75 (A=P, Se) has a low Li+ diffusion barrier and superior electronic conductivity. FeO0.25 S1.75 is more favorable for LiPS adsorption, followed by FeP0.25 S1.75 . FeP0.25 S1.75 (001) shows a low overpotential for the Li-S redox chemistry. In summary, FeP0.25 S1.75 has more application potential in LSBs due to its physical and chemical properties, followed by FeSe0.25 S1.75 . This work provides theoretical guidance for the design and selection of the sulfur cathode host materials in LSBs.

Constructing Metal(II)-Sulfate Site Catalysts toward Low Overpotential Carbon Dioxide Electroreduction to Fuel Chemicals.

Precise regulation of the active site structure is an important means to enhance the activity and selectivity of catalysts in CO2 electroreduction. Here, we creatively introduce anionic groups, which can not only stabilize metal sites with strong coordination ability but also have rich interactions with protons at active sites to modify the electronic structure and proton transfer process of catalysts. This strategy helps to convert CO2 into fuel chemicals at low overpotentials. As a typical example, a composite catalyst, CuO/Cu-NSO4/CN, with highly dispersed Cu(II)-SO4 sites has been reported, in which CO2 electroreduction to formate occurs at a low overpotential with a high Faradaic efficiency (-0.5 V vs. RHE, FEformate=87.4 %). Pure HCOOH is produced with an energy conversion efficiency of 44.3 % at a cell voltage of 2.8 V. Theoretical modeling demonstrates that sulfate promotes CO2 transformation into a carboxyl intermediate followed by HCOOH generation, whose mechanism is significantly different from that of the traditional process via a formate intermediate for HCOOH production.

Photo-Assisted Li-N2 Batteries with Enhanced Nitrogen Fixation and Energy Conversion.

Li-N2 batteries have received widespread attention for their potential to integrate N2 fixation, energy storage, and conversion. However, because of the low activity and poor stability of cathode catalysts, the electrochemical performance of Li-N2 batteries is suboptimal, and their electrochemical reversibility has rarely been proven. In this study, a novel bifunctional photo-assisted Li-N2 battery system was established by employing a plasmonic Au nanoparticles (NPs)-modified defective carbon nitride (Au-Nv -C3 N4 ) photocathode. The Au-Nv -C3 N4 exhibits strong light-harvesting, N2 adsorption, and N2 activation abilities, and the photogenerated electrons and hot electrons are remarkably beneficial for accelerating the discharge and charge reaction kinetics. These advantages enable the photo-assisted Li-N2 battery to achieve a low overpotential of 1.32 V, which is the lowest overpotential reported to date, as well as superior rate capability and prolonged cycle stability (≈500 h). Remarkably, a combination of theoretical and experimental results demonstrates the high reversibility of the photo-assisted Li-N2 battery. The proposed novel strategy for developing efficient cathode catalysts and fabricating photo-assisted battery systems breaks through the overpotential bottleneck of Li-N2 batteries, providing important insights into the mechanism underlying N2 fixation and storage.

Sequentially Regulating Potential-Determining Step for Lowering CO2 Electroreduction Overpotential over Te-Doped Bi Nanotips.

Electrocatalytic conversion of CO2 into formate is recognized an economically-viable route to upgrade CO2, but requires high overpotential to realize the high selectivity owing to high energy barrier for driving the involved proton-coupled electron transfer (PCET) processes and serious ignorance of the second PCET. Herein, we surmount the challenge through sequential regulation of the potential-determining step (PDS) over Te-doped Bi (TeBi) nanotips. Computational studies unravel the incorporation of Te heteroatoms alters the PDS from the first PCET to the second one by substantially lowering the formation barrier for *OCHO intermediate, and the high-curvature nanotips induce enhanced electric field that can steer the formation of asymmetric *HCOOH. In this scenario, the thermodynamic barrier for *OCHO and *HCOOH can be sequentially decreased, thus enabling a high formate selectivity at low overpotential. Experimentally, distinct TeBi nanostructures are obtained via controlling Te content in the precursor and TeBi nanotips achieve >90 % of Faradaic efficiency for formate production over a comparatively positive potential window (-0.57 V to -1.08 V). The strong Bi-Te covalent bonds also afford a robust stability. In an optimized membrane electrode assembly device, the formate production rate at 3.2 V reaches 10.1 mmol h-1 cm-2, demonstrating great potential for practical application.

Dual-Site Bridging Mechanism for Bimetallic Electrochemical Oxygen Evolution.

Heterogeneous dual-site electrocatalysts are emerging cutting-edge materials for efficient electrochemical water splitting. However, the corresponding oxygen evolution reaction (OER) mechanism on these materials is still unclear. Herein, based on a series of in situ spectroscopy experiments and density function theory (DFT) calculations, a new heterogeneous dual-site O-O bridging mechanism (DSBM) is proposed. This mechanism is to elucidate the sequential appearance of dual active sites through in situ construction (hybrid ions undergo reconstruction initially), determine the crucial role of hybrid dual sites in this mechanism (with Ni sites preferentially adsorbing hydroxyls for catalysis followed by proton removal at Fe sites), assess the impact of O-O bond formation on the activation state of water (inducing orderliness of activated water), and investigate the universality (with Co doping in Ni(P4O11)). Under the guidance of this mechanism, with Fe-Ni(P4O11) as pre-catalyst, the in situ formed Fe-Ni(OH)2 electrocatalyst has reached a record-low overpotential of 156.4 mV at current density of 18.0 mA cm-2. Successfully constructed Fe-Ni(P4O11)/Ti uplifting the overall efficacy of the phosphate from moderate to superior, positioning it as an innovative and highly proficient electrocatalyst for OER.

Flattening of Lithium Plating in Carbonate Electrolytes Enabled by All-In-One Separator.

The uncontrollable dendritic growth of metallic lithium during repeated cycling in carbonate electrolytes is a crucial obstacle hindering the practical use of Li-metal batteries (LMBs). Among numerous approaches proposed to mitigate the intrinsic constraints of Li metal, the design of a functional separator is an attractive approach to effectively suppress the growth of Li dendrites because direct contact with both the Li metal surface and the electrolyte is maintained. Here, a newly designed all-in-one separator containing bifunctional CaCO3 nanoparticles (CPP separator) is proposed to achieve the flattening of Li deposits on the Li electrode. Strong interactions between the highly polar CaCO3 nanoparticles and the polar solvent reduces the ionic radius of the Li+ -solvent complex, thus increasing the Li+ transference number and leading to a reduced concentration overpotential in the electrolyte-filled separator. Furthermore, the integration of CaCO3 nanoparticles into the separator induces the spontaneous formation of mechanically-strong and lithiophilic CaLi2 at the Li/separator interface, which effectively decreases the nucleation overpotential toward Li plating. As a result, the Li deposits exhibit dendrite-free planar morphologies, thus enabling excellent cycling performance in LMBs configured with a high-Ni cathode in a carbonate electrolyte under practical operating conditions.

Hierarchical Nanospheres with Polycrystalline Ir&Cu and Amorphous Cu2 O toward Energy-Efficient Nitrate Electrolysis to Ammonia.

Electrochemical reduction reaction of nitrate (NITRR) provides a sustainable route toward the green synthesis of ammonia. Nevertheless, it remains challenging to achieve high-performance electrocatalysts for NITRR especially at low overpotentials. In this work, hierarchical nanospheres consisting of polycrystalline Iridium&copper (Ir&Cu) and amorphous Cu2 O (Cux Iry Oz NS) have been fabricated. The optimal species Cu0.86 Ir0.14 Oz delivers excellent catalytic performance with a desirable NH3 yield rate (YR) up to 0.423 mmol h-1  cm-2 (or 4.8 mg h-1  mgcat -1 ) and a high NH3 Faradaic efficiency (FE) over 90% at a low overpotential of 0.69 V (or 0 VRHE ), where hydrogen evolution reaction (HER) is almost negligible. The electrolyzer toward NITRR and hydrazine oxidation (HzOR) is constructed for the first time with an electrode pair of Cu0.86 Ir0.14 Oz //Cu0.86 Ir0.14 Oz , yielding a high energy efficiency (EE) up to 87%. Density functional theory (DFT) calculations demonstrate that the dispersed Ir atom provides active site that not only promotes the NO3 - adsorption but also modulates the H adsorption/desorption to facilitate the proton supply for the hydrogenation of *N, hence boosting the NITRR. This work thus points to the importance of both morphological/structural and compositional engineering for achieving the highly efficient catalysts toward NITRR.

Exploiting Zirconium-Based Metallic Glass Thin Films for Anode-Free Lithium-Ion Batteries and Lithium Metal Batteries With Ultra-Long Cycling Life.

Coating Zr-based metallic glass, Zr53 Cu31 Ni11 Al5 (Zr-MG), on a Cu current collector (CC) and Li metal anode (LMA) significantly improves the cycle performance of both types of Li-ion batteries, namely, anode-free Li-ion batteries (AFLBs) and Li metal batteries (LMB). The inherent isotropy and homogeneity of the Zr-MG significantly improve the surface uniformity of the CC and LMA. A 12 nm-thick Zr-MG thin film coating on the CC reduces the overpotential in the AFLB, leading to a more uniform Li plating morphology. The Li film covers almost the entire surface of the Zr-CC, whereas it only covers ≈75% of the bare CC during charging. An LFP||Zr-CC full-cell exhibits a capacity retention of 63.6% after the 100th cycle, with an average CE of 99.55% at a 0.2 C rate. In the case of the LMB, a 12 nm-thick Zr-MG thin film-coated LMA (Zr-LMA) exhibits a stable capacity of up to 1500 cycles. An LFP||Zr-LMA full-cell exhibits capacity retention and CE after 1500 cycles of 66.6% and 99.97%, respectively, at a 1 C rate. Zirconium-MG thin films with atomic-level uniformity, outstanding corrosion resistance, lithiophilic characteristics, and high diffusivity result in superior AFLB and LMB performances.

Single-Atom Pd-N4 Catalysis for Stable Low-Overpotential Lithium-Oxygen Battery.

The critical challenge for Li-O2 batteries lies in the large charge overpotential, leading to undesirable side reactions and inferior cycle stability. Single-atom catalysts have shown promising prospects in expediting the kinetics of oxygen evolution reaction (OER) for Li-O2 batteries. However, a present practical drawback is the limited understanding of the correlation between the unique atomic structures and the OER mechanism. Herein, a template-assisted strategy is reported to synthesize atomically dispersed Pd anchored on N-doped carbon spheres as cathode catalysts. Benefiting from the well-defined Pd-N4 moiety, the morphology and distribution of Li2 O2 products are distinctly regulated with optimized decomposition reversibility. Theoretical simulations reveal that the unique configuration of Pd-N4 will contribute to the electron transfer from Pd atoms to the adjacent N atoms, which turns the originally electroneutral Pd into positively charged and downshifts the d-band center and therefore weakens its adsorption energy with the intermediates. The Li-O2 batteries with Pd SAs/NC cathode achieve a charge overpotential of only 0.24 V and sustainable low-overpotential cycling stability (500 mA g-1 ), and can retain a low charge voltage to a very high capacity of 10 000 mAh g-1 . This work provides some insights into designing efficient single-atom catalysts for stable low-overpotential Li-O2 batteries.

Marigold Flower-Shaped Metal-Organic Framework Supported Manganese Vanadium Oxide Electrocatalyst for Efficient Oxygen Evolution Reactions in an Alkaline Medium.

The electrochemical oxygen evolution reaction (OER) is a key process in many renewable energy systems. The development of low-cost, long-lasting alternatives to precious-metal catalysts, particularly functional electrocatalysts with high activity for OER processes, is crucial for reducing the operating expense and complexity of renewable energy generating systems. This work describes a concise method for generating marigold flower-like metal-organic frameworks (MOFs) aided manganese vanadium oxide via a hydrothermal procedure for increased OER activity. As synthesized MOF MnV oxide has a higher surface area due to the 3D flower-like structure, which is reinvented with enhanced electrocatalytic active sites. These distinctive structural features result in remarkable catalytic activity for MOF MnV oxide microflowers towards OER with a low overpotential of 310 mV at 50 mA cm-2 and a Tafel slope with only 51.4 mV dec-1 in alkaline conditions. This study provides a concise method for developing an optimized catalytic material with greater morphology and beneficial features for potential energy and environmental applications.

Recent Progress of Transition Metal Compounds as Electrocatalysts for Electrocatalytic Water Splitting.

Hydrogen has enormous commercial potential as a secondary energy source because of its high calorific value, clean combustion byproducts, and multiple production methods. Electrocatalytic water splitting is a viable alternative to the conventional methane steam reforming technique, as it operates under mild conditions, produces high-quality hydrogen, and has a sustainable production process that requires less energy. Electrocatalysts composed of precious metals like Pt, Au, Ru, and Ag are commonly used in the investigation of hydrogen evolution reaction (HER) and oxygen evolution reaction (OER). Nevertheless, their limited availability and expensive cost restrict practical use. In contrast, electrocatalysts that do not contain precious metals are readily available, cost-effective, environmentally friendly, and possess electrocatalytic performance equal to that of noble metals. However, considerable research effort must be devoted to create cost-effective and high-performing catalysts. This article provides a comprehensive examination of the reaction mechanism involved in electrocatalytic water splitting in both acidic and basic environments. Additionally, recent breakthroughs in catalysts for both the hydrogen evolution and oxygen evolution reactions are also discussed. The structure-activity relationship of the catalyst was deep-going discussed, together with the prospects of current obstacles and potential for electrocatalytic water splitting, aiming at provide valuable perspectives for the advancement of economical and efficient electrocatalysts on an industrial scale.

Shifting Emphasis from Electro- to Catalytically Active Sites: Effects of Pore Size of Flow-Through Anodes on Water Purification.

A flow-through anode has demonstrated high efficiency for micropollutant abatement in water purification. In addition to developing novel electrode materials, a rational design of its porous structure is crucial to achieve high electrooxidation kinetics while sustaining a low cost for flow-through operation. However, our knowledge of the relationship between the pore structure and its performance is still incomplete. Therefore, we systematically explore the effect of pore size (with a median from 4.7 to 49.4 µm) on the flow-through anode efficiency. Results showed that when the pore size was <26.7 µm, the electrooxidation kinetics was insignificantly improved, but the permeability declined dramatically. Traditional empirical evidence from hydrodynamic modeling and electrochemical tests indicated that a flow-through anode with a smaller pore size (e.g., 4.7 µm) had a high mass transfer capability and large electroactive area. However, this did not further accelerate the micropollutant removal. Combining an overpotential distribution model and an imprinting method has revealed that the reactivity of a flow-through anode is related to the catalytically active volume/sites. The rapid overpotential decay as a function of depth in the anode would offset the merits arising from a small pore size. Herein, we demonstrate an optimal pore size distribution (∼20 µm) of typical flow-through anodes to maximize the process performance at a low energy cost, providing insights into the design of advanced flow-through anodes in water purification applications.

Balancing Interfacial Reactions through Regulating p-Band Centers by an Indium Tin Oxide Protective Layer for Stable Zn Metal Anodes.

Metallic zinc (Zn) is considered as one of the most attractive anode materials for the post-lithium metal battery systems owing to the high theoretical capacity, low cost, and intrinsic safety. However, the Zn dendrites and parasitic side reaction impede its application. Herein, we propose a new principle of regulating p-band center of metal oxide protective coating to balance Zn adsorption energy and migration energy barrier for effective Zn deposition and stripping. Experimental results and theoretical calculations indicate that benefiting from the uniform zincophilic nucleation sites and fast Zn transport on indium tin oxide (ITO), highly stable and reversible Zn anode can be achieved. As a result, the I-Zn symmetrical cell achieves highly reversible Zn deposition/stripping with an extremely low overpotential of 9 mV and a superior lifespan over 4000 h. The Cu/I-Zn asymmetrical cell exhibits a long lifetime of over 4000 cycles with high average coulombic efficiency of 99.9 %. Furthermore, the assembled I-Zn/AC full cell exhibits an excellent lifetime for 70000 cycles with nearly 100 % capacity retention. This work provides a general strategy and new insight for the construction of efficient Zn anode protection layer.

Alternating Metal-Ligand Coordination Improves Electrocatalytic CO2 Reduction by a Mononuclear Ru Catalyst.

Molecular electrocatalysts for CO2 -to-CO conversion often operate at large overpotentials, due to the large barrier for C-O bond cleavage. Illustrated with ruthenium polypyridyl catalysts, we herein propose a mechanistic route that involves one metal center that acts as both Lewis base and Lewis acid at different stages of the catalytic cycle, by density functional theory in corroboration with experimental FTIR. The nucleophilic character of the Ru center manifests itself in the initial attack on CO2 to form [Ru-CO2 ]0 , while its electrophilic character allows for the formation of a 5-membered metallacyclic intermediate, [Ru-CO2 CO2 ]0,c , by addition of a second CO2 molecule and intramolecular cyclization. The calculated activation barrier for C-O bond cleavage via the metallacycle is decreased by 34.9 kcal mol-1 as compared to the non-cyclic adduct in the two electron reduced state of complex 1. Such metallacyclic intermediates in electrocatalytic CO2 reduction offer a new design feature that can be implemented consciously in future catalyst designs.

Eliminating Concentration Polarization with Cationic Covalent Organic Polymer to Promote Effective Overpotential of Nitrogen Fixation.

Electrocatalytic nitrogen reduction reaction offers a sustainable alternative to the conventional Haber-Bosch process. However, it is currently restricted by low effective overpotential due to the concentration polarization, which arises from accumulated products, ammonium, at the reaction interface. Here, a novel covalent organic polymer with ordered periodic cationic sites is proposed to tackle this challenge. The whole network exhibits strong positive charge and effectively repels the positively charged ammonium, enabling an ultra-low interfacial product concentration, and successfully driving the reaction equilibrium to the forward direction. With the given potential unchanged, the suppressed overpotential can be much liberated, ultimately leading to a continuous high-level reaction rate. As expected, when this tailored microenvironment is coupled with a transition metal-based catalyst, a 24-fold improvement is generated in the Faradaic efficiency (73.74 %) as compared with the bare one. The proposed strategy underscores the importance of optimizing dynamic processes as a means of improving overall performance in electrochemical syntheses.

Transient Solid-State Laser Activation of Indium for High-Performance Reduction of CO2 to Formate.

Deficiencies in understanding the local environment of active sites and limited synthetic skills challenge the delivery of industrially-relevant current densities with low overpotentials and high selectivity for CO2 reduction. Here, a transient laser induction of metal salts can stimulate extreme conditions and rapid kinetics to produce defect-rich indium nanoparticles (L-In) is reported. Atomic-resolution microscopy and X-ray absorption disclose the highly defective and undercoordinated local environment in L-In. In a flow cell, L-In shows a very small onset overpotential of ≈92 mV and delivers a current density of ≈360 mA cm-2 with a formate Faradaic efficiency of 98% at a low potential of -0.62 V versus RHE. The formation rate of formate reaches up to 6364.4 µmol h-1mgIn-1$mg_{{\rm{In}}}^{--1}$ , which is nearly 39 folds higher than that of commercial In (160.7 µmol h-1mgIn-1$mg_{{\rm{In}}}^{--1}$ ), outperforming most of the previous results that have been reported under KHCO3 environments. Density function theory calculations suggest that the defects facilitate the formation of *OCHO intermediate and stabilize the *HCOOH while inhibiting hydrogen adsorption. This study suggests that transient solid-state laser induction provides a facile and cost-effective approach to form ligand-free and defect-rich materials with tailored activities.