Active Sites Research Articles

Optimizing Hydrazine Activation on Dual‐Site Co‐Zn Catalysts for Direct Hydrazine‐Hydrogen Peroxide Fuel Cells

ABSTRACTDirect hydrazine‐hydrogen peroxide fuel cells (DHzHPFCs) offer unique advantages for air‐independent applications, but their commercialization is impeded by the lack of high‐performance and low‐cost catalysts. This study reports a novel dual‐site Co‐Zn catalyst designed to enhance the hydrazine oxidation reaction (HzOR) activity. Density functional theory calculations suggested that incorporating Zn into Co catalysts can weaken the binding strength of the crucial N2H3* intermediate, which limits the rate‐determining N2H3* desorption step. The synthesized p‐Co9Zn1 catalyst exhibited a remarkably low reaction potential of −0.15 V versus RHE at 10 mA cm−2, outperforming monometallic Co catalysts. Experimental and computational analyses revealed dual active sites at the Co/ZnO interface, which facilitate N2H3* desorption and subsequent N2H2* formation. A liquid N2H4‐H2O2 fuel cell with p‐Co9Zn1 catalyst achieved a high open circuit voltage of 1.916 V and a maximum power density of 195 mW cm−2, demonstrating the potential application of the dual‐site Co‐Zn catalyst. This rational design strategy of tuning the N2H3* binding energy through bimetallic interactions provides a pathway for developing efficient and economical non‐precious metal electrocatalysts for DHzHPFCs.

The Influence of Mg, Na, and Li Oxides on the CO2 Sorption Properties of Natural Zeolite

This study presents a comparative analysis of the CO2 sorption properties of natural zeolites sourced from the Tayzhuzgen (Tg) and Shankanay (Sh) deposits in Kazakhstan. The Tayzhuzgen zeolite was characterized by a Si/Al ratio of 5.6, suggesting partial dealumination, and demonstrated enhanced specific surface area following mechanical activation. Modification of the Tayzhuzgen zeolite with magnesium oxide significantly improved its CO2 sorption capacity, reaching 8.46 mmol CO2/g, attributed to the formation of the CaMg(Si2O6) phase and the resulting increase in basic active sites. TPD-CO2 analysis confirmed that MgO/Tg exhibited the highest basicity of the modified samples, further validating its potential for CO2 capture applications.

Metal‐Phthalocyanine‐Based Two‐Dimensional Conjugated Metal‐Organic Frameworks for Electrochemical Glycerol Oxidation Reaction

Electrochemical glycerol oxidation reaction (GOR) is a promising candidate to couple with cathodic reaction, like hydrogen evolution reaction, to produce high‐value product with less energy consumption. Two‐dimensional conjugated metal‐organic frameworks (2D c‐MOFs), comprising square‐planar metal‐coordination motifs (e.g., MO4, M(NH)4, MS4), are notable for their programable active sites, intrinsic charge transport, and excellent stability, making them promising catalyst candidates for GOR. Here, we introduce a novel class of 2D c‐MOFs electrocatalysts, M2[NiPcS8] (M=Co/Ni/Cu), which are synthesized via coordination of octathiolphthalocyaninato nickel (NiPc(SH)8) with various metal centers. Due to a fast kinetic and high activity of CoS4 sites for GOR, the electrocatalytic tests demonstrate that Co2[NiPcS8] supported on carbon paper displays a low GOR potential of 1.35 V vs. RHE at 10 mA cm‐2, significantly reducing the overall water‐electrolysis‐voltage reduction by 0.27 V from oxygen evolution reaction to GOR, thereby outperforming Ni2[NiPcS8] and Cu2[NiPcS8]. Additionally, we have determined that the GOR activity of CoX4 linkage sites varies with different heteroatoms, following an experimentally and theoretically confirmed activity order of CoS4>CoO4>Co(NH)4. The GOR performance of Co2[NiPcS8] not only demonstrate superior performance among non‐noble metal complex, but also provides critical insights on designing high‐performance MOF electrocatalysts upon optimizing the electronic environment of active sites.

Metal‐Phthalocyanine‐Based Two‐Dimensional Conjugated Metal‐Organic Frameworks for Electrochemical Glycerol Oxidation Reaction

Electrochemical glycerol oxidation reaction (GOR) is a promising candidate to couple with cathodic reaction, like hydrogen evolution reaction, to produce high‐value product with less energy consumption. Two‐dimensional conjugated metal‐organic frameworks (2D c‐MOFs), comprising square‐planar metal‐coordination motifs (e.g., MO4, M(NH)4, MS4), are notable for their programable active sites, intrinsic charge transport, and excellent stability, making them promising catalyst candidates for GOR. Here, we introduce a novel class of 2D c‐MOFs electrocatalysts, M2[NiPcS8] (M=Co/Ni/Cu), which are synthesized via coordination of octathiolphthalocyaninato nickel (NiPc(SH)8) with various metal centers. Due to a fast kinetic and high activity of CoS4 sites for GOR, the electrocatalytic tests demonstrate that Co2[NiPcS8] supported on carbon paper displays a low GOR potential of 1.35 V vs. RHE at 10 mA cm‐2, significantly reducing the overall water‐electrolysis‐voltage reduction by 0.27 V from oxygen evolution reaction to GOR, thereby outperforming Ni2[NiPcS8] and Cu2[NiPcS8]. Additionally, we have determined that the GOR activity of CoX4 linkage sites varies with different heteroatoms, following an experimentally and theoretically confirmed activity order of CoS4>CoO4>Co(NH)4. The GOR performance of Co2[NiPcS8] not only demonstrate superior performance among non‐noble metal complex, but also provides critical insights on designing high‐performance MOF electrocatalysts upon optimizing the electronic environment of active sites.

On the Location and Accessibility of Active Acid Sites in MFI Zeolites Modified by Alkaline Treatment

An MFI zeolite (Si/Al = 40) was desilicated by alkaline treatment in order to generate mesopores. Temperature, alkali concentration and treatment duration were adjusted to maximize mesoporosity while preserving the zeolite structure. Special attention was paid to the characterization of the strength and accessibility of the acid sites. The catalysts were tested in the isobutane/butene alkylation, a reaction that is typically catalyzed by zeolites but limited by coke deposition. Additionally, glycerol esterification with acetic acid was used as a test reaction due to the required participation of large pores. The results confirmed that mesopores were successfully generated in the MFI zeolite, and the diffusion through the solid was enhanced, but the active sites were mainly confined to the micropores.

Na Ions Doped Fe2VO4 Cathode for High Performance Aqueous Zinc-ion Batteries.

Aqueous zinc ion batteries are thought to be a new generation of secondary batteries that will replace lithium-ion batteries due to their great safety and inexpensive cost. In the cathode materials of aqueous zinc ion batteries with long life and high capacity, abundant active sites and crystal structure stability play an important role. In the present work, the strategy of Na+ intercalation of Fe2VO4 (FVO) is proposed, aiming at the insertion of Na+, which not only enriches the active sites, but also sodium and iron ions act as guest species with the negatively charged VOx lattice to provide strong electrostatic attraction to stabilize the lamellar structure. In terms of electrochemical performance, the discharge specific capacity is 370 mAh g-1 at a current density of 0.1 A g-1, and when the current density is arising 5 A g-1, the specific capacity also reaches 200 mAh g-1 after cycling 2000 with a capacity retention of 99 %, which is better than the electrochemical performance of Fe2VO4 (FVO) alone at 50 mAh g-1. The superior electrochemical performance proves that FVO-Na is an ideal cathode material for zinc ion batteries.

Bioassay‐Guided Extraction and Isolation of Natural Herbicides from Dried Zanthoxylum limonella Alston Fruits

AbstractWeeds are problematic plant species around the world. Various strategies exist for controlling weeds, but chemical treatment remains the preferred method, particularly when using natural substances. In this research, a crude aqueous‐methanol extract from dried Zanthoxylum limonella fruits was acid‐base partitioned into four fractions: neutral extract (NE), acid extract (AE), basic extract (BE), and aqueous extract (AQ). These fractions were further separated into seventeen subfractions: NEF1 to NEF7, AEF1 to AEF5, and BEF1 to BEF5, which were then tested for herbicidal activity against the growth of Chinese amaranth (Amaranthus tricolor) and barnyard grass (Echinochloa crus‐galli). Active subfractions were isolated via column chromatography and identified using spectroscopic methods, yielding seven active compounds: xanthoxyline (1), tambulin (2), atanine (3), prudomestin (4), skimmianine (5), p‐methoxybenzoic acid (6), and methyl caffeate (7). Compounds 2–7 had not been previously reported in Z. limonella. Xanthoxyline (1) was identified as the most potent botanical herbicide, fully inhibiting seed germination of Chinese amaranth and barnyard grass. This compound also decreased seed imbibition and α‐amylase activity in both species. Molecular docking studies on the α‐amylase enzyme (PDB ID: 1BG9) revealed that the aromatic, hydroxy, and carbonyl groups of xanthoxyline (1) interact with the enzyme's active sites.

Metal Organic Framework‐Derived Anionic P‐Substitution toward CoNiSe‐P with Excellent Electrochemical Stability for Supercapacitor

AbstractThe regulation of nanostructures and composition can significantly enhance the electrochemical activity and accelerate electrochemical reaction kinetics of electrode material. Herein, metal organic framework(MOF) is used as self‐sacrificing templates to prepare CoNiSe‐P by hydrothermal with following selenylation and phosphorization treatment. Due to the hollow porous structure, rich electrochemical active sites and elements synergistic influence, the obtained CoNiSe‐P electrode shows a high capacity of 838 C g−1, which is much higher than CoNiSe (322 C g−1) and CoNiP (616 C g−1). Furthermore, CoNiSe‐P electrode shows excellent rate characteristic (685 C g−1 at 20 A g−1) and ultrahigh electrochemical stability with capacity retention of 99.6% after 10 000 cycles. More importantly, an asymmetric supercapacitor is assembled with CoNiSe‐P as the positive electrode and nitrogen‐doped porous carbon as the negative electrode delivers an energy density of 42.4 Wh kg−1 at 266.6 W kg−1 and maintains a specific capacitance of 96.8% after 10 000 cycles. Significantly, the asymmetric supercapacitor shows a high energy density up to 21.3 Wh kg−1 at a very high power density of 21.3 kW kg−1, higher than those of previously reported asymmetric supercapacitors.

Stereocatalytic Effect of CeO2 for the Synthesis of trans‐3‐Penten‐2‐ol

AbstractThe transformation of biobased alkanediols over heterogeneous catalysts is a major object. Here, a series of catalysts were prepared for 2,4‐pentanediol dehydration to 3‐penten‐2‐ol. Ceria‐based catalysts had a unique property of showing high efficiency. More importantly, a stereocatalytic effect was observed for CeO2, yielding trans‐3‐penten‐2‐ol with a high selectivity. Raman, XPS, TPD, and TPR were carried out to clarify the catalyst structure, and the relationship between the catalyst structure and catalytic performance were studied. The amount of Lewis acid sites can hardly be correlated with the total concentrations of the oxygen vacancies. It was suggested that the geometry structure of the active sites played a crucial role in trans‐3‐penten‐2‐ol production. The oxygen vacancies originating from CeO2 consisted of active sites with a geometrical structure, which were different from those created by Pr doping CeO2. In addition, the Pr doping enhanced the oxygen migration, which resulted in side reactions, consequently, giving a lower selectivity to trans‐3‐penten‐2‐ol.

Polar Molecule Intercalation to Weaken P2─S Bonding in MnPS3 Toward Ultrahigh-Capacity Sodium Storage.

Layered transition metal trithiophosphates (TMPS3, TM = Mn, Fe, Co, etc.) with high theoretical capacity (>1300 mAh g-1) are potential anode materials for sodium-ion batteries (SIBs). However, the strong bonding between P2 dimers and S atoms in TMPS3 hinders the efficient alloying reaction between P2 dimers and Na+, resulting in practical capacities much lower than theoretical values. Herein, a polar molecule diisopropylamine (DIPA) is intercalated into MnPS3 for the first time to improve the sodium storage performance effectively. Theoretical calculations show that the electron transfer between DIPA and MnPS3 induces more delocalized S p states and weaker P─S bonds, significantly enhancing the electrochemical activity and sodiation/desodiation reaction kinetics. Moreover, the expanded interlayer spacing from 6.48 to 10.75 Å enables faster Na+ diffusion and more active sites for Na+ adsorption. As expected, the DIPA-MnPS3 exhibits an ultrahigh capacity of 1,023 mAh g-1 at 0.2 A g-1 and excellent cycling performance (≈100% capacity retention after 4200 cycles at 10 A g-1), far outperforming those metal thiophosphates anodes reported for SIBs. Interestingly, in situ and ex situ characterizations reveal a quasi-topological intercalation mechanism of DIPA-MnPS3. This work provides a novel strategy for the design of high-performance anode materials for SIBs.

Single-Entity Electrochemistry of N-Doped Graphene Oxide Nanostructures for Improved Kinetics of Vanadyl Oxidation.

N-doped graphene oxides (GO) are nanomaterials of interest as building blocks for 3D electrode architectures for vanadium redox flow battery applications. N- and O-functionalities have been reported to increase charge transfer rates for vanadium redox couples. However, GO synthesis typically yields heterogeneous nanomaterials, making it challenging to understand whether the electrochemical activity of conventional GO electrodes results from a sub-population of GO entities or sub-domains. Herein, single-entity voltammetry studies of vanadyl oxidation at N-doped GO using scanning electrochemical cell microscopy (SECCM) are reported. The electrochemical response is mapped at sub-domains within isolated flakes and found to display significant heterogeneity: small active sites are interspersed between relatively large inert sub-domains. Correlative Raman-SECCM analysis suggests that defect densities are not useful predictors of activity, while the specific chemical nature of defects might be a more important factor for understanding oxidation rates. Finite element simulations of the electrochemical response suggest that active sub-domains/sites are smaller than the mean inter-defect distance estimated from Raman spectra but can display very fast heterogeneous rate constants >1cms-1. These results indicate that N-doped GO electrodes can deliver on intrinsic activity requirements set out for the viable performance of vanadium redox flow battery devices.

The Electron‐Rich Interface Regulated MBene by S‐Bridge Guided to Enhance Nitrogen Fixation under Environmental Conditions

AbstractThe underutilization of active sites limits the performance enhancement of 2D transition metal boride (MBene) in electrocatalytic nitrogen reduction reaction (NRR). Herein, a highly efficient NRR electrocatalyst with S atoms bridging Fe and Mo atoms on the surface of MBene is successfully constructed by using an active site electron optimization strategy, which increases the charge density around the Mo active site and enhances the activation ability of the catalyst to N2 molecules. It is noteworthy that FeS2‐MBene demonstrates a low intrinsic potential for NRR (−0.2 V vs RHE). It is more favorable for the adsorption of nitrogen atoms in comparison to hydrogen atoms, thereby it can effectively inhibit the hydrogen evolution reaction (HER). Under a potential of −0.2 V versus RHE, the ammonia yield rate is 37.13 ± 1.31 µg h−1 mg−1, and the FE is 55.97 ± 2.63%. Density functional theory (DFT) calculations demonstrate that Mo on the surface of MBene serves as a site for the adsorption of N2. The formation of the heterostructure enhances electron transfer, resulting in the Mo active site becoming an electron‐rich state in favor of subsequent hydrogenation steps. This work offers significant insights into the design and utilization of 2D MBene‐based catalysts in NRR.

Densely populated single‐atom catalysts for boosting hydrogen generation from formic acid

AbstractThe single‐atom M‐N‐C (M typically being Co or Fe) is a prominent material with exceptional reactivity in areas of catalysis for sustainable energy. However, the formation of metal nanoparticles in M‐N‐C materials is coupled with high‐temperature calcination conditions, limiting the density of M‐Nx active sites and thus restricting the catalytic performance of such catalysts. Herein, we describe an effective decoupling strategy to construct high‐density M‐Nx active sites by generating polyfurfuryl alcohol in the MOF precursor, effectively preventing the formation of metal nanoparticles even with up to 6.377% cobalt loading. This catalyst showed a high H2 production rate of 778 mL gCat−1 h−1 when used in the dehydrogenation reaction of formic acid. In addition to the high density of the active site, a curved carbon surface in the structure is also thought to be the reason for the high performance of the catalyst.

Ti3+ Self-Doping of TiO2 Boosts Its Photocatalytic Performance: A Synergistic Mechanism

Pollution remains one of the most significant global challenges. Photocatalysis consists of a new organic pollutant removal technology, with TiO2 widely studied as a photocatalyst in the photocatalytic removal of water pollution. However, intrinsic TiO2 has the disadvantages of weak visible light absorption, low electron separation, and transmission efficiency, as well as few active sites. In this study, anatase-phase Ti3+ self-doped TiO2 (B-TiO2) with a core-shell structure was successfully prepared by forming an amorphous layer rich in oxygen vacancies (OVs) and Ti3+ defects on the TiO2 surface under a nitrogen atmosphere using NaBH4 as a chemical-reducing agent. The visible light absorption performance of the catalyst was notably improved when exposed to light irradiation. The bending of surface energy bands facilitated the separation of photogenerated electron-hole pairs, and the core-shell structure allowed the electron-hole pairs to be transported to the surface of the catalyst and participate in the reaction faster. We observed that 92.86% of Rhodamine B (RhB) was degraded in only 5 min, an increase of 2.73 times that of the degradation rate observed in commercial P25. With extraordinary stability, the photocatalytic efficiency of the catalyst remained at 96.2% after five degradation cycles.

Self‐supported thin‐film electrode consisting of transition metal borides for highly efficient hydrogen evolution

AbstractTransition metal borides (TMBs) are a new class of promising electrocatalysts for hydrogen generation by water splitting. However, the synthesis of robust all‐in‐one electrodes is challenging for practical applications. Herein, a facile solid‐state boronization strategy is reported to synthesize a series of self‐supported TMBs thin films (TMB‐TFs) with large area and high catalytic activity. Among them, MoB thin film (MoB‐TF) exhibits the highest activity toward electrocatalytic hydrogen evolution reaction (HER), displaying a low overpotential (η10 = 191 and 219 mV at 10 mA cm−2) and a small Tafel slope (60.25 and 61.91 mV dec−1) in 0.5 M H2SO4 and 1.0 M KOH, respectively. Moreover, it outperforms the commercial Pt/C at the high current density region, demonstrating potential applications in industrially electrochemical water splitting. Theoretical study reveals that both surfaces terminated by TM and B atoms can serve as the active sites and the H* binding strength of TMBs is correlated with the p band center of B atoms. This work provides a new pathway for the potential application of TMBs in large‐scale hydrogen production.

Structure-based discovery of a new type of scaffold compound as binding competitors for protein-bound Uremic Toxins.

Protein-bound uremic toxins (PBUTs) are the main cause of uremia, but traditional hemodialysis is ineffective in removing them because of their strong ability to bind to human serum albumin (HSA), highlighting the need for new treatments. In this study, first, structure-based docking was used to screen a diverse library of 200,376 virtual compounds against the active sites I and II. After two rounds of docking screening, 3944 candidate molecules were obtained. Second, 23 candidate molecules were obtained after ADMET prediction and toxicity analysis. Five candidate molecules were finally obtained after visual analysis and MM-PBSA calculations. We subsequently assessed their competitive displacement efficiency through a microdialysis experiment, and the results revealed that ZINC000008791789, ZINC000012297018, and ZINC000012296493 are promising binding competitors for PBUTs, as they have higher dialysis efficiency than the optimal displacer LA, approximately double the dialysis efficiency. The other two molecules, ZINC000031161007 and ZINC000004090361, although less efficient than LA, still outperformed the control group. Notably, four of them shared the same molecular scaffold, and three of them contained a flavonoid group. These findings provide a foundation for the development of more effective PBUT binding competitors, potentially benefiting uremia patients in the future.

Eco-Friendly High-Performance Symmetric All-COF/Graphene Aqueous Zinc-Ion Batteries.

Developing high-performance aqueous symmetric all-organic batteries (SAOBs) by replacing metal-based batteries or batteries with organic electrolytes is highly attractive to achieve a greener rechargeable world. However, such a new energy storage system still exhibits unsatisfactory rate capability and cycling stability due to the limitations in electrode materials screening. Here, a novel covalent organic framework (COF) containing abundant CN and CO for the electrode material is designed, which is combined with graphene and assembled into all-COF/graphene batteries for the first time. Moreover, the co-storage of Zn2+ and H+ in COF can be achieved in a mild aqueous electrolyte. Impressively, benefiting from the extended porous structure of COF, plentiful active reaction sites, more extensive electron delocalization from CO modification at molecular level, as well as enhanced fast H+ storage capacity of graphene and CO in COF, this kind of SAOBs show excellent cycle life and high rate performance (over 15000 cycles with a capacity of 80 mAh g-1 at a high current density of 5 A g-1 in pouch cell). This work will open a new window for the design of high-performance aqueous organic batteries, further moving toward a more eco-friendly electrochemical world.

Grid-Like Structured Sb@DNC Anode by Self-Sacrificial Etching for Fast and Durable Sodium Storage.

Alloying-type materials are promising anodes for sodium storage due to high specific capacities and appropriate redox potentials, but their practical application is impeded by rapid capacity decay from volume change during sodium ion insertion/extraction. Hence, a dual-type N-doped carbon-confined antimony (Sb) nanoparticle (Sb@DNC, where DNC contains an outer N-doped carbon armor and an inner N-doped grid-like carbon skeleton) anode material is fabricated via a self-sacrificial etching strategy to address this challenge. Specifically, the dual-type N-doped carbon matrix can prevent the agglomeration and precipitation of Sb particles, increase a large number of reactive active sites, alleviate severe volume expansion/contraction, and construct a highly interconnected electron/ion transport network. Benefiting from the exquisite structure, the Sb@DNC electrode exhibits excellent cycling stability (2400 cycles at 1.0 A g-1) and astonishing high-rate performance (331.0 mAh g-1 at 10.0 A g-1). Additionally, the state-of-the-art in/ex situ technologies reveals the sodium storage mechanism of the "battery-capacitance dual-mode" and the origin of the ability to withstand continuous volumetric strain for the Sb@DNC electrode. Finally, the derived sodium-ion full cell presents outstanding practical potential. This work emphasizes the great significance of rational structural engineering strategies in the field of alloy-type anode materials for high-performance sodium-ion batteries.

Crystalline/Amorphous Interface Engineering and d-sp Orbital Hybridization Synergistically Boosting the Electrocatalytic Performance of PdCu Bimetallene toward Formic Acid-Assisted Overall Water Splitting.

Advanced electrocatalysts capable of bifunctional catalysis for formic acid oxidation (FAOR) and hydrogen evolution reaction (HER) have garnered significant attention due to their exceptional energy efficiency. In this research, we have meticulously designed a PdCu bimetallene characterized by numerous crystalline/amorphous (c/a) interfaces and robust d-sp orbital hybridization, achieved by integrating the p-block metalloid boron within the PdCu matrix (B-PdCu-c/a). The B-PdCu-c/a bimetallene revealed a multitude of surface atoms and unsaturated defect sites, offering abundant catalytic active sites and an optimized electronic structure. The B2-PdCu-c/a exhibited the best performance in FAOR and HER, achieving a mass activity of 1106 mA mgcat-1 and an overpotential of 52 mV, respectively. Significantly, the two-electrode configuration of B2-PdCu-c/a∥B2-PdCu-c/a attained a low cell voltage of 0.19 V at 10 mA cm-2 during formic acid-assisted overall water splitting. Density functional theory (DFT) calculations indicated that c/a interface engineering and d-sp orbital hybridization synergistically optimized the electronic configuration of pristine PdCu bimetallene. This led to an elevation of the d-band center and an accumulation of charge at the c/a interface, which enhanced the adsorption of intermediates, facilitated C-H bond cleavage, and balanced the adsorption-desorption of hydrogen, thereby improving electrocatalytic activities for FAOR and HER, respectively. This study not only presents a viable strategy for effectively tuning the electronic configuration of bimetallene but also offers valuable insights into the development of electrocatalysts.

Maximizing Oxygen Evolution Performance of NiFeOx Semitransparent Electrocatalysts Applicable to Photoelectrochemical Water Splitting Device

In photoelectrochemical (PEC) water splitting, semiconductor‐based photoelectrodes can improve reaction rates and durability by incorporating cocatalysts that serve as active sites for the water splitting process. However, achieving both high light transmittance and efficient catalytic activity is essential for these cocatalysts. This study aimed to optimize the surface loading of semitransparent NiFeOx thin‐film electrocatalysts to enhance the oxygen evolution reaction (OER) rates while maintaining high light transmittance. NiFeOx thin films were deposited on fluorine‐doped SnO2 (FTO) transparent conductive substrates, and the relationship between the NiFeOx loading amount (Γ) and the OER rate was examined using electrochemical techniques. The OER rate of NiFeOx on FTO (NiFeOx/FTO) was the highest at a Γ value of 0.20 μmol cm‐2. To further explore the connection between this optimized Γ and PEC activity, the impact of Γ on the PEC OER performance of visible‐light‐absorbing α‐Fe2O3 semitransparent photoanodes was evaluated as a model system. Applying the optimized Γ of NiFeOx to modify the α‐Fe2O3 surface also led to enhanced PEC OER performance. These findings highlight the critical role of surface design, specifically the optimization of cocatalyst loading and electrocatalytic activity, in improving PEC water splitting efficiency, providing valuable guidelines for future semitransparent photoelectrode development.