Dual Modification Research Articles

Revealing the Impact of Dual Site Modification on the Phase Transformation and Ion Transport Mechanism of Ni-Rich Cathode Materials.

Ni-rich cathode materials have garnered significant attention attributable to the high reversible capacity and superior rate performance, particularly in the electric vehicle industry. However, the structural degradation experienced during cycling results in rapid capacity decay and deterioration of the rate performance, thereby impeding the widespread application of Ni-rich cathodes. Herein, a Mg/Ti co-doping strategy was developed to boost the structure stability and Li-ion transport kinetics of the Ni-rich cathode material LiNi0.90Co0.05Mn0.05O2 (NCM9055) under long cycle. It is demonstrated that the Mg2+ ions inserted into the lithium layer could serve as pillars, enhancing the stability of the delithiated layer structure. The introduction of robust Ti-O bonding mitigated the detrimental H2-H3 phase transition (∼4.2 V) during cycling. In addition, despite the fact that Mg/Ti co-doping slightly reduces Li+ diffusion coefficient in the modified cathode material (NCM9055-MT), it effectively stabilized the robustness of the layered structure and maintained the Li+ diffusion channel while charging and discharging, thereby improving the Li+ diffusion coefficient after a long cycle. Therefore, the Mg/Ti co-doped cathode materials exhibited an exceptional capacity retention rate of 99.9% (100 cycles, 1 C). Additionally, the Li+ diffusion coefficient of the co-doped NCM9055-MT (2.924 × 10-10 cm2 s-1) after 100 cycles was effectively enhanced compared with the case of undoped NCM9055 (4.806 × 10-11 cm2 s-1). This work demonstrates that the Mg/Ti co-doping approach effectively enhanced the stability of layered Ni-rich cathode materials.

Caries-Prone Primary Teeth: A Hidden Reason and Prophylactic Treatment in the Viewpoint of Materials Science.

Dental caries, the most prevalent chronic disease across all age groups, has a high prevalence, particularly among children. However, there is no specific and effective treatment for the prevention of caries in primary teeth (Pr.T.), which stems from a lack of knowledge regarding the basic nature of the tooth surface. Herein, we observed that the adhesion energies of the caries-related bacteria Streptococcus mutans and Streptococcus sanguinis to Pr.T were approximately 10 and 5.5 times higher than those to permanent teeth (Pe.T). A lower degree of mineralization and more hydrophilic characteristics of the Pr.T enamel account for this discrepancy. Accordingly, we proposed that the on-target modification of both hydroxyapatite and organic components on Pr.T by dual modification would render a sufficient hydration layer. This resulted in an approximately 11-time decrease in bacterial adhesion energy after treatment. In contrast, a single hydroxyapatite modification on Pe.T and young permanent teeth (Y.Pe.T) was sufficient to achieve a similar effect. Theoretical simulation further verified the rationality of the approach. Our findings may help understand the reason for Pr.T being caries-prone and provide references for treatment using resin restorations. This strategy offers valuable insights into daily oral hygiene and dental prophylactic treatment in children.

Ex-situ catalytic fast pyrolysis of waste polycarbonate for aromatic hydrocarbons: Utilizing HZSM-5/modified HZSM-5

Catalytic pyrolysis has been proven as a highly efficient process for transforming waste polycarbonate (PC) into valuable aromatic hydrocarbons, especially benzene, toluene, ethylbenzene, and xylene (BTEX). In the present work, the ex-situ catalytic fast pyrolysis of PC on metal- or alkali-modified HZSM-5 was investigated using the double micro-fixed bed system. Experimental results indicate that the rapid pyrolysis of PC may follow a homolytic chain scission mechanism, resulting in pyrolysis products dominated by phenols. Metal- or alkali-modified HZSM-5 significantly enhances the cleavage of C-OH bonds in phenols, improving the yield of aromatics. The yield of aromatics in the liquid product is 91 %, 72 %, and 77 % when loaded with nickel (Ni), iron (Fe), and cobalt (Co), respectively, all of which are higher than unmodified HZSM-5 with the yield of 43 %. Among them, the Ni/HZSM-5 has significantly enhanced the yield of BTEX reaching 81.64 %. When using alkali-modified HZSM-5 with a larger pore volume and higher specific surface area, the yield of aromatics can be increased to 60 %. Furthermore, the dual modification of alkali treatment and Ni loading on HZSM-5 simultaneously enhanced catalytic activity and resistance to coke formation. The yield of BTEX reaches 94.47 %. The BTEX formation mechanism can be explained by direct deoxygenation (DDO) of the pyrolytic volatiles of PC and the “phenol pool” mechanisms of primary products on the catalyst surface. This study enriches the understanding of catalytic pyrolysis of PC and provides a theoretical foundation for the harmless treatment of PC.

Dual Modification Strategy for Enhanced Cycling and Rate Performance of Ni-Rich Cathode Materials in Lithium-Ion Batteries.

A great challenge in the commercialization process of layered Ni-rich cathode material LiNixCoyMn1-x-yO2 (NCM, x ≥ 80%) for lithium-ion batteries is the surface instability, which is exacerbated by the increase in nickel content. The high surface alkalinity and unavoidable cathode/electrolyte interface side reactions result in significant decrease for the capacity of NCM material. Surface coating and doping are common and effective ways to improve the electrochemical performance of Ni-rich cathode material. In this study, an in situ reaction is induced on the surface of secondary particles of NCM material to construct a stable lithium sulfate coating, while achieving sulfur doping in the near surface region. The synergistic modification of lithium sulfate coating and lattice sulfur doping significantly reduced the content of harmful residual lithium compounds (RLCs) on the surface of NCM material, suppressed the side reactions between the cathode material surface and electrolyte and the degradation of surface structure of the NCM material, effectively improved the rate capability and cycling stability of the NCM material.

Improving LiFe0.4Mn0.6PO4 Nanoplate Performance by a Dual Modification Strategy toward the Practical Application of Li-Ion Batteries

A novel composite consisting of fluorine-doped carbon and graphene double-coated LiMn0.6Fe0.4PO4 (LMFP) nanorods was synthesized via a facile low-temperature solvothermal method that employs a hybrid glucose and polyvinylidene fluoride as carbon and fluorine sources. As revealed by physicochemical characterization, F-doped carbon coating and graphene form a ‘point-to-surface’ conductive network, facilitating rapid electron transport and mitigating electrochemical polarization. Furthermore, the uniform thickness of the F-doped carbon coating alters the growth of nanoparticles and prevents direct contact between the material and the electrolyte, thereby enhancing structural stability. The strongly electronegative F− can inhibit the structural changes in LMFP during charge/discharge, thus reducing the Jahn–Teller effect of Mn3+. The distinctive architecture of the LMFP/C-F/G cathode material exhibits excellent electrochemical properties, exhibiting an initial discharge capacity of 163.1 mAh g−1 at 0.1 C and a constant Coulombic efficiency of 99.7% over 100 cycles. Notably, the LMFP/C-F/G cathode material achieves an impressive energy density of 607.6 Wh kg−1, surpassing that of commercial counterparts. Moreover, it delivers a reversible capacity of 90.3 mAh g−1 at a high current rate of 5 C. The high-capacity capability and energy density of the prepared materials give them great potential for use in next-generation lithium-ion batteries.

Incorporation anthracene and Cu to NH2-Zr-UiO-67 metal-organic framework: Introducing the simultaneous selectivity and efficiency in photocatalytic CO2 reduction to ethanol

Metal-organic frameworks (MOFs) are considered promising candidates for photocatalytic CO2 reduction (PCR) into valuable organic fuels. However, compared to numerous reports regarding CO, CH4, and CHOOH generation, the explored MOFs have shown limited success in producing alcohols, particularly EtOH, through the PCR strategy. Existing MOFs also suffer from insufficient selectivity and efficiency. This study addresses these limitations by implementing a dual modification strategy on NH2-Zr-UiO-67 MOFs. This strategy involves synthesizing four MOF derivatives with different ratios of redox-active metal sites (Cu) to light absorption antenna (anthracene): 1:1, 2:1, 1:2, and 1:3. The as-synthesized MOFs (denoted as Cu/An (X:X)@NZU67 exhibited a remarkable capability for PCR-to-EtOH, without requiring a photosensitizer. The optimal amount of anthracene plays a crucial role in several aspects: improving light absorption, enhancing CO2 adsorption capacity, and promoting charge transfer/separation. Efficient charge transfer is critical for facilitating the multi-step electron transfer pathway required for ethanol synthesis. Notably, Cu/An (1:2)@NZU67 achieved an ethanol productivity of 624.17 µmolh−1g−1 for EtOH, which is, to the best of our knowledge, the highest efficiency reported for MOFs in PCR-to-EtOH conversion so far. Besides significant performance, the MOF showed 100% selectivity for EtOH production. This work represents a significant milestone in the field of PCR-to-EtOH transformation by providing a new perspective for designing MOF photocatalysts that can simultaneously improve both selectivity and efficiency.

LC-MS characterization of N/O-glycans of α- and β-subunits of chicken ovomucin separated by SDS-PAGE

As the main active glycoprotein of egg white, the biological functions of chicken ovomucin α- and β-subunit are closely related to the structure of glycans. However, the exact composition and structure of the subunit glycans are still unknown. We obtained highly pure chicken ovomucin α-subunit and β-subunit protein bands by the strategy combined with two-step isoelectric precipitation and SDS-PAGE gel electrophoresis. The ammonia-catalyzed one-pot procedure was then used to release and capture α-and β-subunit protein glycans with 1-phenyl- 3-Methyl-5-pyrazolone (PMP). The N/O-glycans of bis-PMP derivatives were purified and analyzed by LC-MS. More importantly, an effective dual modification was performed to accurately quantify neutral and sialylated O-glycans through methylamidation of sialic acid residues and simultaneously through carbonyl condensation reactions of reducing ends with PMP. We first showed that the α-subunit protein has only N-glycosylation modification, and the β-subunit only O-glycosylation, a total of 22 N-glycans and 20 O-glycans were identified in the α- and β-subunit, respectively. In addition, the complex N-glycan (47 %) and the sialylated O-glycan (77 %) are each major types of the above subunits. Such findings in this study provide a basis for studying the functional and biological activities of chicken ovomucin glycans.

Ultrahigh electrochemical properties of Na3V2(PO4)3 under synergistic effects of Er3+ substitution and CNTs coating

Currently, the low ionic and electronic conductivities of Na3V2(PO4)3 (NVP) have been hindered its further application. In this paper, a simultaneous optimized method of Er3+ substitution and carbon nanotubes (CNTs) enwrapping is proposed for the first time. Due to the large ionic radius of Er3+ (89 pm vs 64 pm of V3+), Er3+ occupying the position of V3+ makes the crystal structure more stable and alleviates the deformation of the crystal cell. Meanwhile, the interplanar spacing of NVP is broadened after introducing Er3+, so the de-intercalation rate of Na+ can be accelerated and the kinetic properties are improved. In addition, the enwrapped CNTs connecting with amorphous carbon layers construct a conductive substrate for the fast electronic transportation, which significantly modifies the electronic conductivity. Moreover, the CNTs benefits to inhibit the agglomeration of NVP active materials and make the distribution more uniform and grain size more smaller. The decreasing size indicates a shorter pathway for Na+ migration, which improves its apparent ionic diffusivity. Through the above analysis, the dual modification strategy can efficiently improve the kinetic properties of NVP system. Notably, Na3V1.93Er0.07(PO4)3/C@CNTs (NVEP-0.07) submits a high capacity of 84.2 mAh g−1 at 50 C and maintains 70.6 mAh g−1 after 8000 cycles, corresponding to a high retention ratio of 83.9 %. The assembled NVEP-0.07//CHC full cell reveals 146.2 mAh g−1 at 0.1 C, which successfully lightens the LED bulbs, indicating the excellent application potential of NVEP-0.07. Impressively, the recycled XRD/SEM/XPS results demonstrate the significantly improved crystal stability and chemical state of NVEP-0.07.

Surface reconstructed layer with bulk high-valence Mo doping to achieve long-life LiMn2O4 cathode material

Mo doping plays a striking role in the stability enhancement of LiMn2O4 cathode materials. However, the underlying microscopic mechanism is still unclear. Here, we elucidate that the relationship between the atomic position of Mo doping in LiMn2O4 and the stability enhancement of Mo-doped LiMn2O4 by utilizing the spherical aberration-corrected scanning transmission electron microscopy (Cs-STEM). It exhibits that the part of Mo6+ ions occupy empty Mn 16c site to form a surface reconstructed layer of rock-salt like phase on the outermost surface and other Mo6+ ions dope into the Mn octahedral 16d sites to form LiMoxMn2-xO4 in bulk, which is beneficial for inhibiting the parasitic side reactions. Concomitantly, this dual modification of bulk structure and surface can significantly enhance electrode reversibility and Li+ diffusion. As a result, excellent long cycling stability of the as-designed optimal LiMo0.01Mn1.99O4 after 1500 cycles with 61.61 % capacity retention at 10 C (1 C = 148 mAh g−1) is presented, with an initial discharge capacity of 88.30 mAh g−1. Our research provides a clever approach for regulating the surface structure/bulk architecture in LiMn2O4 cathode materials.

Dual genetic level modification engineering accelerate genome evolution of Corynebacterium glutamicum.

High spontaneous mutation rate is crucial for obtaining ideal phenotype and exploring the relationship between genes and phenotype. How to break the genetic stability of organisms and increase the mutation frequency has become a research hotspot. Here, we present a practical and controllable evolutionary tool (oMut-Cgts) based on dual genetic level modification engineering for Corynebacterium glutamicum. Firstly, the modification engineering of transcription and replication levels based on RNA polymerase α subunit and DNA helicase Cgl0854 as the 'dock' of cytidine deaminase (pmCDA1) significantly increased the mutation rate, proving that the localization of pmCDA1 around transient ssDNA is necessary for genome mutation. Then, the combined modification and optimization of engineering at dual genetic level achieved 1.02×104-fold increased mutation rate. The genome sequencing revealed that the oMut-Cgts perform uniform and efficient C:G→T:A transitions on a genome-wide scale. Furthermore, oMut-Cgts-mediated rapid evolution of C. glutamicum with stress (acid, oxidative and ethanol) tolerance proved that the tool has powerful functions in multi-dimensional biological engineering (rapid phenotype evolution, gene function mining and protein evolution). The strategies for rapid genome evolution provided in this study are expected to be applicable to a variety of applications in all prokaryotic cells.

Promoting the Photoelectrochemical Properties of BiVO4 Photoanode via Dual Modification with CdS Nanoparticles and NiFe-LDH Nanosheets.

Bismuth vanadate (BiVO4) has long been considered a promising photoanode material for photoelectrochemical (PEC) water splitting. Despite its potential, significant challenges such as slow surface water evolution reaction (OER) kinetics, poor carrier mobility, and rapid charge recombination limit its application. To address these issues, a triadic photoanode has been fabricated by sequentially depositing CdS nanoparticles and NiFe-layered double hydroxide (NiFe-LDH) nanosheets onto BiVO4, creating a NiFe-LDH/CdS/BiVO4 composite. This newly engineered photoanode demonstrates a photocurrent density of 3.1 mA cm-2 at 1.23 V vs. RHE in 0.1 M KOH under AM 1.5 G illumination, outperforming the singular BiVO4 photoanode by a factor of 5.8 and the binary CdS/BiVO4 and NiFe-LDH/BiVO4 photoanodes by factors of 4.9 and 4.3, respectively. Furthermore, it exhibits significantly higher applied bias photon-to-current efficiency (ABPE) and incident photon-to-current efficiency (ICPE) compared to pristine BiVO4 and its binary counterparts. This enhancement in PEC performance is ascribed to the formation of a CdS/BiVO4 heterojunction and the presence of a NiFe-LDH OER co-catalyst, which synergistically facilitate charge separation and transfer efficiencies. The findings suggest that dual modification of BiVO4 with CdS and NiFe-LDH is a promising approach to enhance the efficiency of photoanodes for PEC water splitting.

Dual modification of current collector for high-performance lithium metal batteries by laser etching

Despite the lithium metal anode is regarded as the next generation of anode for its high energy density and low redox potential, the huge volume expansion and high reactivity between lithium and electrolyte still limit its application. Herein, a multilayer Cu current collector is designed to accommodate the volume expansion and suppress the high reactivity. Through laser etching, the structure and the chemical component of Cu foil are deeply changed. Planar Cu is etched to construct regular microstructure with different length in interval, which regulate the current density distribution and alleviate the massive volume expansion during the charging process. And the surface of microstructure reacts with air to form lithiophilic phase CuxO layer in situ resulting in stable surface of lithium metal anodes. The simple dual-modification strategy enables the half-cell to achieves a cycle life of over 240 cycles with the CE above 98%. In contrast, the initial Cu only achieve a cycle life of less than 50 cycles. Meanwhile, full battery based on multilayer current collector delivered outstanding cycle stability. This work shows an innovative sight for the modification of current collector and safe Li metal anode.

Bi & Mo co-doped In2S3 nano-foam blocks for boosted photocatalytic hydrogen generation

The design and construction of dual modifications on photocatalysts is a promising strategy to improve the photocatalytic properties. Herein, we fabricated the In2S3 nano-foam blocks with dual modifications of Bi & Mo co-doping and structure construction via a simple hydrothermal method to achieve an enhanced photocatalytic hydrogen generation. The results reveal that Bi & Mo co-doped In2S3 nano-foam blocks exhibit a high hydrogen generation rate of 5.45 mmol/g/h, which is 27 times that of bulk In2S3. Owing to the structural advantages, the enhanced specific surface area of the as-prepared nano-foam blocks improve the light harvesting efficiency of photocatalytic system. More importantly, the doped Bi and Mo atoms boost the improvement in the transfer and separation of photogenerated electrons and holes by introducing the impurity energy level. This work provides a reliable strategy for the design and fabrication of high-efficiency photocatalytic reaction system.

Garnet conductor network with Zr doping to implement surface bifunctional modification for Ni-rich cathodes

High‑nickel oxides are promising cathode materials for next-generation lithium batteries due to their high discharge capacity. LiNi0.83Co0.11Mn0.06O2(NCM83), a polycrystalline material widely used for its excellent performance, faces challenges such as interfacial side reactions and lattice oxygen release that hinder its electrochemical performance under high voltage. To promote the high-voltage performance of NCM83, Li7La3Zr2O12, a fast ion conductor with high conductivity and a wide electrochemical window, is taken into account. Here, the oxidation reaction and element diffusion are employed during high-temperature sintering to realize dual functional modification of NCM83 materials, including La-rich conductor network construction and near-surface Zr doping. Impressively, the modified electrode shows excellent cycling performance with 82.14 % retention after 200 cycles at 2.8–4.6 V, and splendid rate capability. Detailed studies reveal that ZrO bonds inhibit the migration of transition metal ions, preventing the distortion of the material structure. The surface ionic conductor network layer provides fast Li+ diffusion channels and protects the interfacial layer from electrolyte decomposition products. The facile Li7La3Zr2O12 modification method proposed in this paper is suitable for solving the interfacial and structural stability of cathode materials, offering hope for the application of high-energy lithium-ion batteries.

A new bi-directional surface modification cathode based on conventional cathode La0.6Sr0.4Co0.2Fe0.8O3-δ

The commercialization of proton solid oxide fuel cells (H-SOFCs) is hindered by the lack of high active and durable cathode materials exposed to evil operation conditions. Here, this groundbreaking study addresses two critical challenges impeding the practicality of La0.6Sr0·4Co0·2Fe0·8O3-δ (LSCF), one of the most popular proton-conducting cathode materials contemporarily: inadequate temperature activity and durability issues stemming from surface Sr segregation. The research introduces a transformative solution through the creation of a novel nanofiber cathode, denoted as PrBaCo1.4Fe0·6O6-δ@LSCF, comprising a nanoscale LSCF FP host and PBCF NP guest. Advanced electron microscopy and scanning electron microscopy techniques confirm the seamless integration of the two phases, highlighting a distinctive fiber structure adorned with impregnated nanoparticles. Meanwhile, efficiently reducing oxygen vacancies within the LSCF bulk phase significantly suppresses Sr segregation. Systematic simulations based on density functional theory reveal that the incorporation of PSCF reduces the polarization energy barrier. In practical terms, electrochemical testing of a single cell supported by PBCF@LSCF shows a polarization resistance of only 0.053 Ω cm2 at 700 °C, translating to a remarkable fifty percent reduction. Furthermore, a sustained 100-h test reveals no notable decline in performance. Consequently, a novel dual modification approach is proposed for crafting cathodes tailored for SOFCs.

Stereospecific Synthesis and Biological Evaluation of KRN7000 Analogues with Thio-modifications at the Acyl Moiety.

α-Galactosylceramide (KRN7000 or α-GalCer) analogues terminated with phenyl (Ph) groups at the acyl moiety possess more potency than KRN7000 to activate invariant natural killer T (iNKT) cells for inducing a T helper 1 (Th1)-biased immune response. However, biological activities of phenyl glycolipids with thio-modifications at the acyl moiety remain unknown, and facile approaches for highly stereoselective synthesis of KRN7000 and its analogues are rather scarce. Herein, we exploited 4,6-di-O-tert-butylsilylene (DTBS)-directed stereospecific galactosylation to efficiently synthesize various α-GalCer analogues bearing thioamide, terminal thiophenyl and dual modifications at the acyl moiety. Biological evaluations suggest that a new analogue S34 featuring a terminal Ph-S-Ph-F group exhibits a more superior Th1-biased immune response in mice. Molecular docking analysis revealed that the introduction of a sulfur atom influences vital hydrogen bonding interactions between glycolipids and the cluster of differentiation 1d (CDld), thus adjusting the stability of the glycolipid-CDld complex.

Effect of Single and Dual Modifications on the Physicochemical Properties of Sago Starch Modified by Ozonation and Acetylation

Abstract Dual-step starch modification is an effort to eliminate weaknesses in single-step modification. This research aims to study the effect of single-step or dual-step modification methods on the physicochemical properties of sago starch. The single step consists of ozonation (Oz) and acetylation (As), while the dual step (sequentially), namely ozonation-acetylation (Oz-As) and acetylation-ozonation (As-Oz). The physiochemical responses measured were water content, carbonyl content, carboxyl content, acetyl content, water solubility index (WSI), water absorption index (WAI), and color. Ozonation causes the formation of carbonyl and carboxyl groups, and the modification process certainly causes the addition of carbonyl and carboxyl groups both in single step and dual-step. Acetylation causes higher acetyl group values in either single-step (As) or dual step (Oz-As and As-Oz) compared to original sago starch. There was a significant difference between the single and dual steps in the WSI and WAI values. The characteristics of Ozonated-acetylated (Oz-As) modified sago showed starch the highest WSI and WAI results. The water content in single-step modified sago starch compared to native sago starch has no significant difference in water content, whereas the dual-step modified sago starch has a higher water content than the native one.

Dual interfacial modification with 1D perovskite for self-assembled monolayer based inverted perovskite solar cells

Recently, self-assembled monolayer (SAM) based inverted perovskite solar cells (PSCs) have been extensively studied due to their remarkable stability and compatibility with large-area devices. Microporesat the SAM/perovskite buried interface are commonly observed, which result in the increased defect density and hindered charge extraction. Herein, a multifunctional organic material, namely 2-(methylthio)-4,5-dihydro-1 H-imidazole ammonium iodide (MTIm), is introduced as an interfacial modification material to react with the residual PbI2, forming one-dimensional (1D) (MTIm)PbI3 small grains. We found that the 1D perovskite distributes at both top and buried interfaces of PSC, achieving dual-interfacial passivation of defects. Moreover, the 1D perovskite leads to a favorable n-type doping at the top interface, and relaxes the lattice strain at the buried interface. As a result, the champion PSC device achieves significantly improved power conversion efficiency from 21.7 % to 23.8 %, and retains over 90 % of its initial PCE after storing in air for 1500 hours.

The dual modification of La and Zr of Ni-rich cathodes for improved cycling stability at elevated voltage and temperature

Nickel-rich layered oxides are regarded as a promising cathode material for next-generation lithium-ion batteries (LIBs) with advanced power capabilities. However, their poor cycling performance, especially under high voltage and temperature conditions, has seriously limited their large-scale application. In this work, a simple and effective strategy is proposed to enhance the structural and interface stability of Ni-rich materials by La4NiLiO8 coating and Zr doping. The interfacial side reactions and intergranular microcracks of the modified material are inhibited, which is helpful in improving the electrochemical performance. Therefore, the initial capacity of dual modification of La and Zr of Ni-rich cathode is 196.4 mA h g−1 at 4.5 V and exhibits excellent cycling performance with a capacity retention of 82.1 % after 200 cycles. Moreover, at 50 °C, the initial capacity of the modified material is 239.0 mA h g−1, and the capacity retention is 63.1 % after 100 cycles, representing a significant improvement of 94.8 % over the unmodified sample.

Activating MnO2 nanosheet arrays for accelerated water oxidation through the synergic effect of Ni loading and O vacancies

Birnessite (δ-MnO2), inspired by biological photosynthesis, holds promise as oxygen evolution reaction (OER) catalysts in water electrolysis for clean energy. Given that Mn3+ serves as the active sites, various strategies have been employed to increase the Mn3+ content to boost the OER activity. To surpass the limitations of the traditional adsorbate evolution mechanism (AEM), we have adopted an electrochemical reduction method to introduce metallic Ni and enrich oxygen vacancies onto δ-MnO2 nanosheets. The resulting Ni/MnO2v/CC exhibits exceptional OER performance, with a reduction in overpotential by 190 mV (from 478 mV to 289 mV) at 10 mA cm−2 and a Tafel slope as low as 45 mV dec-1, indicating accelerated catalytic activity. Experimental and theoretical analyses attribute this enhancement to a transition from the traditional AEM to lattice oxygen mechanism (LOM) mechanism. Moreover, the dual modification also enhances electronic conductivity, electrochemical surface area, and charge transfer ability of δ-MnO2. Our work offers a pathway to overcome conventional limitations in OER electrocatalysts, applicable not only to Mn-based catalysts but also to a range of other transition metal oxides.