Lattice Oxygen Research Articles

Greenly Synthesized Conducting Polymer Nanotunnels with Metal-Hydroxide Nanobundles in Single Dais for Unmitigated Water Oxidation.

Electrochemical water splitting required efficient electrocatalysts to produce clean hydrogen fuel. Here, we adopted greenway coprecipitation (GC) method to synthesize conducting polymer (CP) nanotunnel network affixed with luminal-abluminal CoNi hydroxides (GC-CoNiCP), namely, GC-Co1Ni2CP, GC-Co1.5Ni1.5CP, and GC-Co2Ni1CP. The active catalyst, GC-Co2Ni1CP/GC, has low oxygen evolution reaction (OER) overpotential (307 mV) and a smaller Tafel slope (47 mV dec-1) than IrO2 (125 mV dec-1). The electrochemical active surface area (EASA) normalized linear sweep voltammetry (LSV) curve exhibited outstanding intrinsic activity of GC-Co2Ni1CP, which required 285 mV to attain 10 mA cm-2. At 1.54 V, the estimated turnover frequency (TOF) of GC-Co2Ni1CP/GC (0.017337 s-1) was found to be 3-fold higher than that of IrO2 (0.0014 s-1). Furthermore, the GC-Co2Ni1CP/NF consumed a very low overpotential (281 mV) with a small Tafel slope of 121 mV dec-1. The ultrastability of GC-Co2Ni1CP for industrial application was confirmed by durability at 10 and 100 mA cm-2 for the OER (GC/NF-8 h, 2.0%/100 h, 2.2%) and overall water splitting (100 h, 3.8%), which implies that GC-Co2Ni1CP had adequate kinetics to address the elevated rates of water oxidation. The effect of pH and addition of tetramethylammonium cation (TMA+) reveal that GC-Co2Ni1CP follows the lattice oxygen mechanism (LOM). The solar-powered water electrolysis at 1.55 V supports the efficacy of GC-Co2Ni1CP in the solar-to-hydrogen conversion. The environmental impact studies and solar-driven water electrolysis proved that GC-CoNiCP has excellent greenness and efficiency, respectively.

Polyoxometalates‐Mediated Selectivity in Pt Single‐Atoms on Ceria for Environmental Catalysis

AbstractOptimizing the reactivity and selectivity of single‐atom catalysts (SACs) remains a crucial yet challenging issue in heterogeneous catalysis. This study demonstrates selective catalysis facilitated by a polyoxometalates‐mediated electronic interaction (PMEI) in a Pt single‐atom catalyst supported on CeO2 modified with Keggin‐type phosphotungstate acid (HPW), labeled as Pt1/CeO2‐HPW. The PMEI effect originates from the unique arrangement of isolated Pt atoms and HPW clusters on the CeO2 support. Electrons are transferred from the ceria support to the electrophilic tungsten in HPW clusters, and subsequently, Pt atoms donate electrons to the now electron‐deficient ceria. This phenomenon enhances the positive charge of Pt atoms, moderating O2 activation and limiting lattice oxygen mobility compared to the conventional Pt1/CeO2 catalyst. The resulting electronic structure of Pt combined with the strong and local acidic environment of HPW on Pt1/CeO2‐HPW leads to improved efficiency and N2 selectivity in the degradation of NH3 and NO, as well as increased CO2 yield when inputting volatile organic compounds. This study sheds the light on the design of SACs with balanced reactivity and selectivity for environmental catalysis.

Metalloid Phosphorus Induces Tunable Defect Engineering in High Entropy Oxide Toward Advanced Lithium‐Ion Batteries

AbstractThe inferior electrical conductivity and sluggish lithium storage kinetics of conventional high‐entropy oxide (HEO) are critical issues hindering their commercialization. The high electronegativity of metalloids can ameliorate this predicament by altering the electronic configuration of HEO compared to metals. Herein, metalloid phosphorus doping in spinel‐type HEO (PxA1‐x)B2O4 (A/B = Cr, Mn, Fe, Co, Ni) (P‐HEO) is achieved through a facile sol–gel process. The metalloid phosphorus doping facilitates the transfer of electrons from transition metal sites to phosphorus‐doped sites, resulting in the formation of electron‐rich and electron‐deficient local regions on the HEO surface and is conducive to an increase in the total number of active lithium sites in the electrochemical reaction process. Density functional theory calculation reveals Li adsorption energy on the synthesized P‐HEO is only −1.102 eV, demonstrating that the phosphorus doping enables a strong electronic coupling between lithium ions and P‐HEO. Furthermore, metalloid phosphorus doping also leads to oxygen vacancies formation and lattice distortion, which significantly enhances charge transfer efficiency and diffusion kinetics and results in the enhanced lithium storage performance with impressive rate capability and long‐term stability. These findings provide valuable insights for the design of lattice‐engineered HEO as versatile electrodes for future energy storage applications.

Balancing Layered Ordering and Lattice Oxygen Stability for Electrochemically Stable High-Nickel Layered Cathode for Lithium-ion Batteries

Despite the high-capacity nature of high-nickel cathode materials, achieving their practical implementation is challenging due to the susceptibility of atomic arrangement to calcining conditions. Extensive studies have enlightened the correlation between layered ordering and calcining conditions; nevertheless, the alterations in the electronic structure of lattice oxygen remain obscure. In this study, by comparing cathode materials with varying degrees of layered ordering, achieved through adjustments in calcination temperature and lithium equivalent, it is shown that although layered ordering increases, it compromises the electronic structure, creating a labile lattice oxygen environment. Fine structural analysis reveals that a higher local Li/O ratio in highly ordered cathode subsequently alters the band structure by narrowing the band gap between Ni 3d and O 2p, which enhances transition metal–oxygen covalency, and reduces the oxygen vacancy formation energy, adversely affecting cyclability. In highly ordered cathode, the tendency of lattice oxygen to reside within a Li-enriched environment arises from the changes in the favorability of non-paired antisite defects contingent upon the calcination temperature and lithium equivalent. This research underscores the need to balance layered ordering and lattice oxygen stability, offering important insights for the future design of high-nickel cathodes.

A DFT study on the sulfur resistance mechanism of elemental mercury catalytic oxidation over Mn-Mo/CNT

The strong sulfur resistance of Mn-Mo/CNT during the process of elemental mercury catalytic oxidation at low temperature has been demonstrated in experiment. However, there remains a dearth of in-depth research on the sulfur resistance mechanism. This work aims to explore the sulfur resistance mechanism through density functional theory (DFT) calculations. The results reveal that SO2 can be effectively oxidized to SO3 through lattice oxygen on the surface of Mn-Mo/CNT. The speed control step is the step of SO3 dissociation, with an energy barrier of 2.50 eV. Additionally, O2 can adsorb onto active sites to supplement the consumed lattice oxygen. The adsorbed O2 can also oxidize SO2, and the highest energy barrier of this reaction is only 0.26 eV. SO3 can further react with the adsorbed Hg0 to form HgSO4, and the speed control step is the step of Hg0 oxidation. Specifically, when Hg0 is adsorbed onto Mo active sites, its energy barrier of speed control step reaches 4.06eV. Whereas, when Hg0 is adsorbed on Mn site, the energy barrier of speed control step reduces to 3.18eV. Generally, the coupling reaction process of Hg0 oxidation and SO2/SO3 conversion over Mn-Mo/CNT is the reason of the promotion in sulfur resistance of this catalyst.

Porous and defective NiCo2O4 spinel derived from bimetallic NiCo-based Prussian blue analogue for enhanced hydrogen production via the urea electro-oxidation reaction

The efficient hydrogen production via overall water splitting is seriously restrained by the slow kinetics of the oxygen evolution reaction (OER). The substantially low potential for the urea electro-oxidation reaction (UOR) can tackle this problem by replacing the OER at the electrolyzer anode. Herein, the NiCo2O4 spinel with rich oxygen vacancies (Ov) and embedded within mesoporous carbon network (Ov-NiCo2O4@mC) was derived from NiCo-based Prussian blue analogous (NiCo PBA) and exploited as the bifunctional electrocatalyst of the UOR and OER for boost the hydrogen production via the overall water splitting. Benefiting to the regular skeleton and abundant dual metal sites of NiCo PBA, the derived Ov-NiCo2O4@mC comprises abundant oxygen vacancies, lattice defects, and adjustable electron structure. These features afford Ov-NiCo2O4@mC the improved UOR ability, showing the potential of 1.33 V versus reversible hydrogen electrode (RHE) at the current density of 10 mA cm−2, along with a small Tafel slopes of 31 mV dec-1, remarkably lower than that of the OER (1.51 V versus RHE, Tafel slope = 85 mV dec-1). The UOR performance of Ov-NiCo2O4@mC substantially outperforms to most of the reported Co and/or Ni-based electrocatalysts. Impressively, the assembled two-electrode urea-assisted overall water splitting device shows the small voltage for the hydrogen production (1.43 V versus RHE) and good long-term stability. The present work can provide a new alternative for the efficient hydrogen production using the MOFs-derivatives.

Crystal Modulation of Mn-Based Layered Oxide toward Long-Enduring Anionic Redox with Fast Kinetics for Sodium-Ion Batteries.

Mn-based layered oxide cathodes for sodium-ion batteries with anionic redox reactions hold great potential for energy storage applications due to their ultra-high capacity and cost effectiveness. However, achieving high capacity requires overcoming challenges such as oxygen-redox failure, sluggish kinetics, and structural degradation. Herein, we employ an innovative crystal modulation strategy, using Mn-based Na0.72Li0.24Mn0.76O2 as a representative cathode material, which shows that the highly exposed {010} active facets enable an enhanced rate capability (119.6 mAh g-1 at 10C) with fast kinetics. Meanwhile, the reinforced Mn-O bond inhibits excessive oxidation of lattice oxygen and O-O cohesion loss, stabilizing and maintaining a long-enduring reversible oxygen-redox activity (100% high capacity retention after 100 cycles at 0.5C and 84.28% retention after 300 cycles at 5C). Time-resolved operando two-dimensional X-ray diffraction reveals the robust structural stability, zero-strain behavior, and suppressed phase transition with ultra-low volume variation during cycling at different rates (0.1C: 1.75%, 1C: 0.31%, 5C: 0.04%). Additionally, the full cell coupled with hard carbon achieves a high energy density of approximately 211 Wh kg-1 with superior performance. This work highlights the significance of crystal modulation and presents a universal approach in developing Mn-based oxide cathodes with stable anionic redox for high-performance sodium-ion batteries.

Crystal Modulation of Mn‐Based Layered Oxide toward Long‐Enduring Anionic Redox with Fast Kinetics for Sodium‐Ion Batteries

Mn‐based layered oxide cathodes for sodium‐ion batteries with anionic redox reactions hold great potential for energy storage applications due to their ultra‐high capacity and cost effectiveness. However, achieving high capacity requires overcoming challenges such as oxygen‐redox failure, sluggish kinetics, and structural degradation. Herein, we employ an innovative crystal modulation strategy, using Mn‐based Na0.72Li0.24Mn0.76O2 as a representative cathode material, which shows that the highly exposed {010} active facets enable an enhanced rate capability (119.6 mAh g−1 at 10C) with fast kinetics. Meanwhile, the reinforced Mn–O bond inhibits excessive oxidation of lattice oxygen and O–O cohesion loss, stabilizing and maintaining a long‐enduring reversible oxygen‐redox activity (100% high capacity retention after 100 cycles at 0.5C and 84.28% retention after 300 cycles at 5C). Time‐resolved operando two‐dimensional X‐ray diffraction reveals the robust structural stability, zero‐strain behavior, and suppressed phase transition with ultra‐low volume variation during cycling at different rates (0.1C: 1.75%, 1C: 0.31%, 5C: 0.04%). Additionally, the full cell coupled with hard carbon achieves a high energy density of approximately 211 Wh kg−1 with superior performance. This work highlights the significance of crystal modulation and presents a universal approach in developing Mn‐based oxide cathodes with stable anionic redox for high‐performance sodium‐ion batteries.

Continuous lattice oxygen participation of NiFe stack anode for Sustainable water Splitting

Non-noble anode catalysts exhibit insufficient activity and stability for anion exchange membrane water electrolysis (AEMWE). Accordingly, we propose an electrolyte additive strategy involving NiFe-layered double hydroxide. In situ Raman spectroscopy and 18O isotope labeling experiments reveal that Fe ions in the electrolyte change the oxygen evolution reaction mechanism from adsorbate evolution to the lattice oxygen participation mechanism (LOM). These Fe ions continuously refill Fe vacancies owing to facile metal dissolution via the LOM. In a unit cell, we achieve an excellent cell voltage of 1.73 V and energy conversion efficiency (ECE) of 69.4 % at 3.0 A cm−2, meeting the target set by the U.S. Department of Energy (1.80 V and 69.0 % ECE). Our optimized membrane electrode assembly enhances the cell activity (1.567 V at 1.0 A cm−2; ECE = 76.5 %) and stability (0.125 mVcell h−1 at 0.5 A cm−2 for 500 h) with a 100 cm2 AEMWE stack.

The Role and Substitution of Cobalt in the Cobalt‐Lean/Free Nickel‐Based Layered Transition Metal Oxides for Lithium Ion Batteries

AbstractThe Nickel‐based layered transition metal oxide cathode represented by NCM (LiNixCoyMnzO2, x+y+z=1) and NCA (LiNixCoyAlzO2, x+y+z=1) is widely used in the electric vehicle market due to its specific capacity and high working potential, in which Cobalt (Co) plays a huge role in improving the structural stability during the cycle. However, the limited supply of Co, due to its scarcity and the influence of geopolitics, poses a significant constraint on the further advancement of the Nickel‐based layered transition metal oxide cathode in the field of energy storage. In this paper, the mechanism of Co in the Nickel‐based layered transition metal oxides is reviewed, including its critical role for structural stability such as the inhibition of cationic mixing and the release of lattice oxygen et al. Subsequently, it outlines various strategies to enhance the performance of Co‐lean/free materials, such as ion doping, including single‐ion doping and multi‐ion co‐doping, and various surface coating strategies, so as to eliminate the adverse effects of Co loss on materials. Ultimately, this paper offers a glimpse into the promising future of Cobalt‐free strategies for high performance of Nickel‐based layered transition metal oxides.

Reversible Configurations of 3-Coordinate and 4-Coordinate Boron Stabilize Ultrahigh-Ni Cathodes with Superior Cycling Stability for Practical Li-Ion Batteries.

Ultrahigh-Ni layered oxide cathodes are the leading candidate for next-generation high-energy Li-ion batteries owing to their cost-effectiveness and ultrahigh capacity. However, the increased Ni content causes larger volume variations and worse lattice oxygen stability during cycling, resulting in capacity attenuation and kinetics hysteresis. Herein, a Li2SiO3-coated Li(Ni0.95Co0.04Mn0.01)0.99B0.01O2 ultrahigh-Ni cathode that well-addresses all the above issues, which is also the first time to realize the real doping of B ions is demonstrated. The as-obtained cathode delivers a reversible capacity of up to 237.4 mAh g-1 (924 Wh kg-1 cathode) and a superior capacity retention of 84.2% after 500 cycles at 1C in pouch-type full-cells. Advanced characterizations and calculations verify that the boron-doping is existed in terms of 3-coordinate and 4-coordinate configurations and their high electrochemical reversibility during de-/lithiation, which greatly stabilizes oxygen anions and impedes Ni-ion migration to Li layer. Furthermore, the B-doping engineers the primary particle microstructure for better relaxing the lattice strain and accelerating Li-ion diffusion. This work advances the energy density of cathode materials into the domain of above 900 Wh kg-1, and the concept will inspire more intensive study on ultrahigh-Ni cathodes.

Toward High-Performance Li-Rich Mn-Based Layered Cathodes: A Review on Surface Modifications.

Lithium-rich manganese-based layered oxides (LRMOs) have received attention from both the academic and the industrial communities in recent years due to their high specific capacity (theoretical capacity ≥250 mAhg-1), low cost, and excellent processability. However, the large-scale applications of these materials still face unstable surface/interface structures, unsatisfactory cycling/rate performance, severe voltage decay, etc. Recently, solid evidence has shown that lattice oxygen in LRMOs easily moves and escapes from the particle surface, which inspires significant efforts on stabilizing the surface/interfacial structures of LRMOs. In this review, the main issues associated with the surface of LRMOs together with the recent advances in surface modifications are outlined. The critical role of outside-in surface decoration at both atomic and mesoscopic scales with an emphasis on surface coating, surface doping, surface structural reconstructions, and multiple-strategy co-modifications is discussed. Finally, the future development and commercialization of LRMOs are prospected. Looking forward, the optimal surface modifications of LRMOs may lead to a low-cost and sustainable next-generation high-performance battery technology.

Understanding the Different Roles of Adsorbed Oxygen and Lattice Oxygen Species in the Distinct Catalytic Performance of Metal Oxides for o-Xylene Oxidation

Understanding the Different Roles of Adsorbed Oxygen and Lattice Oxygen Species in the Distinct Catalytic Performance of Metal Oxides for <i>o</i>-Xylene Oxidation

Engineering Lattice Oxygen Regeneration of NiFe Layered Double Hydroxide Enhances Oxygen Evolution Catalysis Durability.

The lattice oxygen mechanism (LOM) endows NiFe layered double hydroxide (NiFe-LDH) with superior oxygen evolution reaction (OER) activity, yet the frequent evolution and sluggish regeneration of lattice oxygen intensify the dissolution of active species. Herein, we overcome this challenge by constructing the NiFe hydroxide/Ni4Mo alloy (NiFe-LDH/Ni4Mo) heterojunction electrocatalyst, featuring the Ni4Mo alloy as the oxygen pump to provide oxygenous intermediates and electrons for NiFe-LDH. The released lattice oxygen can be timely offset by the oxygenous species during the LOM process, balancing the regeneration of lattice oxygen and assuring the enhancement of the durability. In consequence, the durability of NiFe-LDH is significantly enhanced after the modification of Ni4Mo with an impressively durability for over 60 h, much longer than that of NiFe-LDH counterpart with only 10 h. In-situ spectra and first-principle simulations reveal that the adsorption of OH- is significantly strengthened owing to the introduction of Ni4Mo, ensuring the rapid regeneration of lattice oxygen. Moreover, NiFe-LDH/Ni4Mo-based anion exchange membrane water electrolyzer (AEMWE) presents an impressive durability for over 150 h at 100 mA cm-2. The oxygen pump strategy opens opportunities to balance the evolution and regeneration of lattice oxygen, enhancing the durability of efficient OER catalysts.

Engineering Lattice Oxygen Regeneration of NiFe Layered Double Hydroxide Enhances Oxygen Evolution Catalysis Durability

The lattice oxygen mechanism (LOM) endows NiFe layered double hydroxide (NiFe‐LDH) with superior oxygen evolution reaction (OER) activity, yet the frequent evolution and sluggish regeneration of lattice oxygen intensify the dissolution of active species. Herein, we overcome this challenge by constructing the NiFe hydroxide/Ni4Mo alloy (NiFe‐LDH/Ni4Mo) heterojunction electrocatalyst, featuring the Ni4Mo alloy as the oxygen pump to provide oxygenous intermediates and electrons for NiFe‐LDH. The released lattice oxygen can be timely offset by the oxygenous species during the LOM process, balancing the regeneration of lattice oxygen and assuring the enhancement of the durability. In consequence, the durability of NiFe‐LDH is significantly enhanced after the modification of Ni4Mo with an impressively durability for over 60 h, much longer than that of NiFe‐LDH counterpart with only 10 h. In‐situ spectra and first‐principle simulations reveal that the adsorption of OH− is significantly strengthened owing to the introduction of Ni4Mo, ensuring the rapid regeneration of lattice oxygen. Moreover, NiFe‐LDH/Ni4Mo‐based anion exchange membrane water electrolyzer (AEMWE) presents an impressive durability for over 150 h at 100 mA cm−2. The oxygen pump strategy opens opportunities to balance the evolution and regeneration of lattice oxygen, enhancing the durability of efficient OER catalysts.

Mitigating the Kinetic Hysteresis of Co-Free Ni-Rich Cathodes via Gradient Penetration of Nonmagnetic Silicon.

Co-free Ni-rich layered oxides are considered a promising cathode material for next-generation Li-ion batteries due to their cost-effectiveness and high capacity. However, they still suffer from the practical challenges of low discharge capacity and poor rate capability due to the hysteresis of Li-ion diffusion kinetics. Herein, based on the regulation of the lattice magnetic frustration, the Li/Ni intermixing defects as the primary origin of kinetic hysteresis are radically addressed via the doping of the nonmagnetic Si element. Meanwhile, by adopting gradient penetration doping, a robust Si-O surface structure with reversible lattice oxygen evolution and low lattice strain is constructed on Co-free Ni-rich cathodes to suppress the formation of surface dense barrier layer. With the remarkably enhanced Li-ion diffusion kinetics in atomic and electrode particle scales, the as-obtained cathodes (LiNixMn1-xSi0.01O2, 0.6≤x≤0.9) achieve superior performance in discharge capacity, rate capability, and durability. This work highlights the coupling effect of magnetic structure and interfacial chemicals on Li-ion transport properties, and the concept will inspire more researchers to conduct an intensive study.

Surface Cladding Engineering via Oxygen Sulfur Distribution for Stable Electrocatalytic Oxygen Production

AbstractInevitable leaching and corrosion under anodic oxidative environment greatly restrict the lifespan of most catalysts with excellent primitive activity for oxygen production. Here, based on Fick’ s Law, we present a surface cladding strategy to mitigate Ni dissolution and stabilize lattice oxygen triggering by directional flow of interfacial electrons and strong electronic interactions via constructing elaborately cladding‐type NiO/NiS heterostructure with controlled surface thickness. Multiple in situ characterization technologies indicated that this strategy can effectively prevent the irreversible Ni ions leaching and inhibit lattice oxygen from participating in anodic reaction. Combined with density functional theory calculations, we reveal that the stable interfacial O−Ni−S arrangement can facilitate the accumulation of electrons on surficial NiO side and weaken its Ni−O covalency. This would suppress the overoxidation of Ni and simultaneously fixing the lattice oxygen, thus enabling catalysts with boosted corrosion resistance without sacrificing its activity. Consequently, this cladding‐type NiO/NiS heterostructure exhibits excellent performance with a low overpotential of 256 mV after 500 h. Based on Fick's law, this work demonstrates the positive effect of surface modification through precisely adjusting of the oxygen‐sulfur exchange process, which has paved an innovative and effective way to solve the instability problem of anodic oxidation.

Improved Catalytic Partial Oxidation of Methane via Lattice Oxygen Modification on Supported Copper Oxide Catalyst System

AbstractThirteen kinds of supported copper oxide catalysts (Cu/MOx, MOx: La2O3, Al2O3, SiO2, TiO2, CeO2, ZrO2, SnO2, SrCO3, BaCO3, Ta2O5, Nb2O5, WO3, and MoO3), which form Cu−O−M sites at the interface between CuOx and MOx or within the complex oxides (CuMOx), were tested for CH4 partial oxidation to find out catalytically active Cu−O−M combinations for production of CH3OH and HCHO. Among the thirteen Cu/MOx tested, Cu/WO3 exhibited the highest total yield of CH3OH and HCHO in a CH4‐O2‐H2O flow reaction at 400 °C. The structural and property analysis of Cu/WO3 revealed the formation of CuWO4, of which the lattice oxygen is active for the partial oxidation of CH4.

Mitigating the Kinetic Hysteresis of Co‐Free Ni‐Rich Cathodes via Gradient Penetration of Nonmagnetic Silicon

AbstractCo‐free Ni‐rich layered oxides are considered a promising cathode material for next‐generation Li‐ion batteries due to their cost‐effectiveness and high capacity. However, they still suffer from the practical challenges of low discharge capacity and poor rate capability due to the hysteresis of Li‐ion diffusion kinetics. Herein, based on the regulation of the lattice magnetic frustration, the Li/Ni intermixing defects as the primary origin of kinetic hysteresis are radically addressed via the doping of the nonmagnetic Si element. Meanwhile, by adopting gradient penetration doping, a robust Si−O surface structure with reversible lattice oxygen evolution and low lattice strain is constructed on Co‐free Ni‐rich cathodes to suppress the formation of surface dense barrier layer. With the remarkably enhanced Li‐ion diffusion kinetics in atomic and electrode particle scales, the as‐obtained cathodes (LiNixMn1−xSi0.01O2, 0.6≤x≤0.9) achieve superior performance in discharge capacity, rate capability, and durability. This work highlights the coupling effect of magnetic structure and interfacial chemicals on Li‐ion transport properties, and the concept will inspire more researchers to conduct an intensive study.

Activating d10 electronic configuration to regulate p-band centers as efficient active sites for solar energy conversion into H2 by surface atomic arrangement

Relationship between the activity for photocatalytic H2O overall splitting (HOS) and the electron occupancy on d orbits of the active component in photocatalysts shows volcanic diagram, and specially the d10 electronic configuration in valley bottom exhibits inert activity, which seriously fetters the development of catalytic materials with great potentials. Herein, In d10 electronic configuration of In2O3 was activated by phosphorus atoms replacing its lattice oxygen to regulate the collocation of the ascended In 5p-band (In ɛ5p) and descended O 2p-band (O ɛ2p) centers as efficient active sites for chemisorption to *OH and *H during forward HOS, respectively, along with a declined In 4d-band center (In ɛ4d) to inhibit its backward reaction. A stable STH efficiency of 2.23% under AM 1.5 G irradiation at 65 °C has been obtained over the activated d10 electronic configuration with a lowered activation energy for H2 evolution, verified by femtosecond transient absorption spectroscopy, in situ diffuse reflectance infrared Fourier transform spectroscopy and theoretical calculations of dynamics. These findings devote to activating d10 electronic configuration for resolving the reaction energy barrier and dynamical bottleneck of forward HOS, which expands the exploration of high-efficiency catalytic materials.