Catalytic Reaction Research Articles

Photoinduced synthesis of ultrafine Pt nanoparticles loaded on the surface of MOFs-modified carbon materials for efficient catalytic reduction reactions

Abstract In this paper, ultrafine platinum nanoparticles (Pt/Co-N-C) were prepared by irradiating the mixture of Co-N-C and K2[PtCl4] with near-ultraviolet (UV) light at a wavelength of 395 nm and visible light at 450 and 550 nm without adding any reducing and stabilizing agents using MOFs-modified carbon materials (Co-N-C) as the carrier. The composition and morphology of the Pt/Co-N-C catalysts were investigated using characterization tools such as X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FT-IR), X-ray photoelectron spectroscopy (XPS), and high-resolution transmission electron microscopy (HR-TEM), etc. The results showed that the Pt nanoparticles were well dispersed on the surface of the Co-N-C, with average particle sizes of about 2.39, 2.86, and 3.53 nm, respectively. In the catalytic 4-NP reduction experiments, the catalyst (Pt/Co-N-C-1) prepared under near-ultraviolet light (395 nm) irradiation showed the highest catalytic activity with a rate constant k=0.64 min-1. After five cycles, the conversion rate was still maintained at about 90%, which was highly reusable. It was demonstrated that 395 nm near-ultraviolet light was more favorable for the modulation of the distribution of the species during the hydrolysis and reduction of platinum in this reaction to form smaller-sized platinum nanocrystals, which was conducive to the catalyst to exhibit higher activity.

Asymmetric multi-component trifunctionalization reactions with α-Halo Rh-carbenes

Multi-component multi-functionalization reactions involving active intermediates are powerful tools for rapidly generating a wide array of compounds. Metal carbynoids, with their distinct reactivity, hold great promise for developing synthetic methodologies. However, their application in catalytic transfer reactions has been hindered by the limited availability of suitable precursors. In this study, we investigate the catalytic potential of α-halo Rh-carbenes, leveraging the concept of metal carbynoids in multi-functionalization reactions. Through a chiral phosphoric acid-catalyzed asymmetric trifunctionalization, we have developed a method for synthesizing a variety of chiral α-cyclic ketal β-amino esters with high yields and excellent enantioselectivity. Our extensive experimental and computational studies reveal that α-halo Rh-carbenes exhibit carbynoid properties, which facilitate the transformation into functionalized Fischer-type Rh-carbenes through the decomposition of the C-halo bond.

Efficient PET Depolymerization Using Cost‐Effective Alkali and Alkaline Earth Metal‐Based Salts for High Monomer Yield

AbstractCatalytic glycolysis of polyethylene terephthalate (PET) into its monomer, bis(2‐hydroxyethyl) terephthalate (BHET), is a major focus of chemical research in recent decades. Metal catalysts, especially heavy metal salts, are recognized for their efficiency in degrading this widely used thermoplastic. However, concerns over the non‐biodegradable and toxic nature of heavy metal catalysts like Zn and Pb salts, along with their limited selectivity, have led researchers to seek alternative, more environmentally friendly, and cost‐effective catalysts. This study explores alternatives such as lithium, sodium, and calcium acetate/formates, demonstrating that selected benign metal salts not only accelerate PET degradation but can also surpass traditional heavy metal acetate catalysts (e.g., Zn acetate) in terms of activity and BHET yield. More importantly, complete PET conversion is achieved within 3 h at ≈188 °C, with excellent BHET yield. The catalytic reactions using lithium and calcium acetate show a superior initial reaction rate under optimized conditions.

Endogenous Iron(II) Self-Enriched Fenton Nanocatalyst via FTH1 Activity Inhibition and Iron(III) Reduction for Amplified Cancer Ferroptosis Therapy.

Due to the increased expression of iron storage proteins in cancer cells, utilizing the endogenous iron-catalyzed Fenton reaction for cancer ferroptosis therapy has recently emerged as a prominent research focus. However, endogenous iron primarily exists within ferroxidase FTH1 in the Fe (III)-bound state, hindering the effective catalysis of the Fenton reaction. Herein, an endogenous iron(II) self-enriched Fenton nanocatalyst (BAI@cLANCs) is fabricated by encapsulating the FTH1 inhibitor baicalin (BAI) in cross-linked lipoic acid nanocarriers (cLANCs) to amplify endogenous ferroptosis. Once internalized, BAI@cLANCs are disrupted by glutathione (GSH) in tumor cells to release BAI, which inhibits FTH1 activity and hinders Fe2+ oxidation. Meanwhile, cLANCs degrade into dihydrolipoic acid (DHLA), which reduces Fe3+ to Fe2+, synergically enriching endogenous Fe2+. Simultaneously, both BAI and DHLA stimulate H2O2 production and facilitate the Fenton reaction to produce abundant ·OH, thereby triggering lipid peroxidation and inducing tumor ferroptosis. Moreover, the reduction of Fe3+ to Fe2+ depletes GSH, facilitating ·OH production and inactivating glutathione peroxidase-4, ultimately amplifying tumor ferroptosis. Overall, this work highlights the potential of an endogenous iron(II) self-enriched Fenton nanocatalyst for cancer ferroptosis therapy, providing a paradigm for amplifying endogenous ferroptosis by inhibiting FTH1 activity and reducing iron(III) to enrich endogenous iron(II).

Biosynthesis of unique natural product scaffolds by Fe(II)/αKG-dependent oxygenases.

Fe(II)/αKG-dependent oxygenases are multifunctional oxidases responsible for the formation of unique natural product skeletons. Studies of these enzymes are important because the knowledge of their catalytic functions, enzyme structures, and reaction mechanisms can be used to create non-natural enzymes through mutation and synthesize non-natural compounds. In this review, I will introduce the research we have conducted on two fungal Fe(II)/αKG-dependent oxygenases, TlxI-J and TqaL. TlxI-J is the first Fe(II)/αKG-dependent oxygenase type enzyme heterodimer that catalyzes consecutive oxidation reactions, hydroxylation followed by retro-aldol or ketal formation, to form the complex skeletons of meroterpenoids. TqaL is the first naturally occurring aziridine synthase, and I will discuss the mechanism of its unique C-N bond formation in nonproteinogenic amino acid biosynthesis. This review will advance research on the discovery of new enzymes and the analysis of their functions by reviewing the structures and functions of these extraordinary Fe(II)/αKG-dependent oxygenases, and promote their use in the synthesis of new natural medicines.

Spatial Confinement of a Dual Activatable DNAzyme Sensor in the Cavity of a DNA Nanocage for Logic‐Gated Molecular Imaging

AbstractDespite intense interest in design of DNAzyme sensors for molecular detection and imaging in living cells, their intracellular applications are still hampered by limited spatial control and poor bio‐stability. Here we present controlled spatial confinement of a rationally designed, microRNA (miRNA)‐activatable DNAzyme sensor probe (mDz) within the cavity of DNA nanocage, enabling efficient intracellular delivery with improved bio‐stability for AND‐gate molecular imaging. The mDz that possesses inactive DNAzyme activity is designed by the introduction of a blocking DNA strand, while miR‐21 mediated strand displacement reaction allows for the formation of an intact DNAzyme structure for metal‐ion‐mediated catalytic reaction. Furthermore, the DNA nanocage serves as a nanocarrier for intracellular delivery of mDz, in which the cavity is accessible to the dual targets for logic‐gated molecular imaging, while the confinement effect can provide steric protection of mDz by obstructing nuclease from entering the cavity of the DNA nanocage, resulting in enhanced bio‐stability and improved molecular imaging precision. This strategy paves a way for the engineering of activatable DNA nanosensors with both self‐delivery and self‐protection capabilities to detect diverse intracellular targets.

Theoretical Insights into Rare-Earth-Catalyst-Controlled Diastereo- and Enantioselective [3 + 2] Annulation of Aromatic Aldimines with Styrenes.

Rare-earth-catalyzed annulation reactions using alkenes via C-H activation offer an atom-efficient approach to constructing cyclic compounds. However, the mechanisms underlying these reactions remain poorly understood, limiting the rational design of related catalytic systems. Recently, Hou and Cong reported an unprecedented example of rare-earth-catalyst-controlled diastereodivergent asymmetric [3 + 2] annulation of aromatic aldimines with alkenes. To elucidate the mechanisms and the origins of diastereo- and enantioselectivity, density functional theory calculations were performed. The results revealed that the styrene insertion step determines the stereoselectivity. Styrene insertion follows a similar metal-styrene interaction pattern across different catalysts. Specifically, during cis-insertion, styrene interacts strongly with the metal center, exhibiting significant Sc···Ph interactions, whereas such interactions are absent during trans-insertion. Thus, when the catalyst is employed with a small ligand, stereoselectivity is primarily governed by electronic factors, favoring the cis-insertion mode. In contrast, for the more sterically hindered catalyst, the Sc···Ph interactions in cis-insertion are insufficient to overcome the steric effects, leading to a preference for the trans-insertion mode, which minimizes steric hindrance. These findings offer deeper insights into the origins of catalyst-controlled diastereo- and enantioselectivity and will also contribute to the rational design of stereospecific annulation reactions in rare-earth catalysis.

An atomically economical and environmentally benign approach for the scalable synthesis of rare‐earth metal‐organic framework catalysts

AbstractMetal–organic frameworks (MOFs), as an emerging class of porous materials, demonstrated substantial potential for applications in chemical engineering processes. However, their production often generates significant waste including ionic residues and organic solvents, posing considerable environmental concerns. Herein, we report the environmentally benign MOF synthesis with metal oxides precursors, yielding water as the exclusive by‐product. This approach not only enhances atom economy but also promotes solvent recycling by preventing anion accumulation, significantly reducing waste generation. The synthesis can be easily scaled up in a 10‐L reactor with an impressive space–time yield of 608 kg·m−3·day−1. Furthermore, MOF‐76(Y) was implemented in a reactor for catalytic cycloaddition reaction at kg‐scale. Through optimization of the interfacial contact between CO2 and the reaction liquid phase, a yield of 96.7% was achieved under mild conditions. This work demonstrates a rare example of scalable and sustainable synthesis of MOF materials coupled with catalysis implementation at kilogram scale.

Resourceful Hydrogen Generation through Methanol Steam Reforming Using Rare-Earth Metal Oxide-Modified Delafossite 3D Hollow Spheres.

The world is moving toward the goal of achieving net-zero carbon emissions by 2050, and hydrogen energy is considered an excellent alternative to nonrenewable energy sources. In this regard, developing a catalyst that is both economically valuable and exhibits efficient hydrogen production is a primary task at the current stage. This study utilized a hydrothermal synthesis method to prepare a nanosized 3-dimensional (3D) hollow sphere of CuCrO2-CeO2 for use in the Steam Reforming of Methanol (SRM) process. The characteristics and morphology of prepared CuCrO2-CeO2 hollow sphere were characterized by using various techniques such as XRD, FESEM, HRTEM, FTIR, Raman, etc. The CuCrO2-CeO2 hollow spheres with a 1:2 ratio exhibited the highest hydrogen production efficiency at 550 °C, yielding 6372.73 mL STP min-1 g cat-1 per gram of catalyst. Furthermore, the incorporation of CeO2 not only enhanced the hydrogen production rate of CuCrO2 but also extended the applicability of CuCrO2 nanoparticles to a wider temperature range. The unique 3D hollow sphere structure of the catalyst offers numerous advantages such as low cost, multiple catalytic reaction sites, and easy preparation. Therefore, CuCrO2-CeO2 hollow spheres hold potential for commercial development.

Mechanism of Hydrogen Generation Catalyzed by a Single Atom and Its Spin Regulation.

Single-atom catalysts exhibit the excellent catalytic activity and selectivity, making them widely applicable in the fields of advanced materials, environmental science, and chemical synthesis. However, understanding the mechanism of single-atom catalytic reactions, such as the hydrogen generation reaction, is still challenging, which notably hampers the optimization and precise control of the reaction. Here, we immobilize a single-metal atom model catalyst into a single-molecule electrical detection platform for in situ monitoring of the catalytic hydrogen generation process at the single-event level. In combination with theoretical and experimental studies, the catalytic mechanisms of the hydrogen generation reaction, especially the selection of the catalytic center through charge, spin, and orbital quantum control, are elucidated. In addition, a hydrogen generation process via quantum spin-induced catalysis is observed, in which the turnover frequency increases by about 65 times at a magnetic field of 50 mT. This study provides valuable insights into the intrinsic mechanism of single-metal atom catalysis and opens up unique avenues for their precise control, thus offering a useful strategy for efficiently developing clean energy.

Evolution and Reconstruction of Air-Electrode Surface Composition in Reversible Protonic Ceramic Cells: Mechanisms, Impacts on Catalytic Performance, and Optimization Strategies - A Review.

Reversible protonic ceramic cells (R-PCCs) are at the forefront of electrochemical conversion devices, capable of reversibly and efficiently converting chemical energy into electricity at intermediate temperatures (350-700°C) with zero carbon emissions. However, slow surface catalytic reactions at the air-electrode often hinder their performance and durability. The electrode surface is not merely an extension of the bulk structure, equilibrium reconstruction can lead to significantly different crystal-plane terminations and morphologies, which are influenced by material's intrinsic properties and external reaction conditions. Understanding electrode surface evolution at elevated temperatures in water-containing, oxidative atmospheres presents significant importance. In this review, a comprehensive summary of recent processes in applying advanced characterization techniques for high-temperature electrode surfaces is provided, exploring the correlations between surface evolution and performance fluctuations by examining the structural evolution and reconstruction of various air-electrode surfaces associated with degradation and activation phenomena, offering insights into their impact on electrode performance. Furthermore, reported strategies and recent advances in enhancing the electrochemical performance of R-PCCs through engineering air-electrode surfaces is discussed. This review offers valuable insights into surface evolution in R-PCCs and is expected to guide future developments in high-temperature catalysis, solid-state ionics, and energy materials.

Selectively monitoring the operando temperature of active metal nanoparticles during catalytic reactions by X-ray absorption nanothermometry

Selectively monitoring the operando temperature of active metal nanoparticles during catalytic reactions by X-ray absorption nanothermometry

Improving the Methane Oxidation by Self‐Adaptive Optimization of Liquid‐Metal Catalysts

Methane, a major greenhouse gas and abundant carbon resource, presents significant challenges in catalysis due to its high symmetry and thermodynamic stability, which tend to cause over‐oxidation to CO2. Traditional catalysts require high temperatures and pressures to facilitate CH4 conversion, constrained by their rigid structures which lack the flexibility needed for optimizing complex reaction steps. This study introduces a novel Cu single atoms‐embedded liquid metal catalyst (Cu‐LMC) based on gallium alloys, characterized by dynamic, self‐adaptive structures that provide enhanced catalytic performance and selectivity. Our findings reveal that Cu‐LMC achieves a high methane conversion to methanol yield (5.9 mol·gCu‐1·h‐1) with a selectivity of 82%. The results show that mild surface oxidation significantly boosts the catalytic performance of Cu‐LMC by increasing active copper sites through the formation of a Cu‐O‐Ga configuration while preserving the catalyst's structural flexibility. In‐situ XPS and XAFS analyses, along with AIMD simulations, demonstrate that the Cu‐LMC enables self‐adaptive structural adjustments that lower methanol desorption energy and increase the energy barrier for by‐product formation, optimizing the overall methane conversion process. The results underscore the importance of designing catalysts with dynamic and adaptable structures to overcome traditional limitations and improve efficiency in catalytic reactions.

Improving the Methane Oxidation by Self-Adaptive Optimization of Liquid-Metal Catalysts.

Methane, a major greenhouse gas and abundant carbon resource, presents significant challenges in catalysis due to its high symmetry and thermodynamic stability, which tend to cause over-oxidation to CO2. Traditional catalysts require high temperatures and pressures to facilitate CH4 conversion, constrained by their rigid structures which lack the flexibility needed for optimizing complex reaction steps. This study introduces a novel Cu single atoms-embedded liquid metal catalyst (Cu-LMC) based on gallium alloys, characterized by dynamic, self-adaptive structures that provide enhanced catalytic performance and selectivity. Our findings reveal that Cu-LMC achieves a high methane conversion to methanol yield (5.9 mol·gCu-1·h-1) with a selectivity of 82%. The results show that mild surface oxidation significantly boosts the catalytic performance of Cu-LMC by increasing active copper sites through the formation of a Cu-O-Ga configuration while preserving the catalyst's structural flexibility. In-situ XPSand XAFSanalyses, along with AIMD simulations, demonstrate that the Cu-LMC enables self-adaptive structural adjustments that lower methanol desorption energy and increase the energy barrier for by-product formation, optimizing the overall methane conversion process. The results underscore the importance of designing catalysts with dynamic and adaptable structures to overcome traditional limitations and improve efficiency in catalytic reactions.

Spatial Confinement of a Dual Activatable DNAzyme Sensor in the Cavity of a DNA Nanocage for Logic-Gated Molecular Imaging.

Despite intense interest in design of DNAzyme sensors for molecular detection and imaging in living cells, their intracellular applications are still hampered by limited spatial control and poor bio-stability. Here we present controlled spatial confinement of a rationally designed, microRNA (miRNA)-activatable DNAzyme sensor probe (mDz) within the cavity of DNA nanocage, enabling efficient intracellular delivery with improved bio-stability for AND-gate molecular imaging. The mDz that possesses inactive DNAzyme activity is designed by the introduction of a blocking DNA strand, while miR-21 mediated strand displacement reaction allows for the formation of an intact DNAzyme structure for metal-ion-mediated catalytic reaction. Furthermore, the DNA nanocage serves as a nanocarrier for intracellular delivery of mDz, in which the cavity is accessible to the dual targets for logic-gated molecular imaging, while the confinement effect can provide steric protection of mDz by obstructing nuclease from entering the cavity of the DNA nanocage, resulting in enhanced bio-stability and improved molecular imaging precision. This strategy paves a way for the engineering of activatable DNA nanosensors with both self-delivery and self-protection capabilities to detect diverse intracellular targets.

H-Bonds in Carbon Quantum Dot-anchored C3N5 to Boost Proton-Coupled Electron Transfer for Piezoelectric-Driven Hydrogen Peroxide Synthesis under Ambient Conditions.

Tuning proton-coupled electron transfer (PCET) is a promising strategy to boost the oxygen reduction reaction (ORR) for H2O2 synthesis, but the slow transmission rate of protons and electrons to active sites remains a significant bottleneck. To address this, we developed an H-bond-driven PCET process based on carbon quantum dotanchored C3N5 (CQDs-C3N5) for piezo-catalytic H2O2 synthesis. CQD-C3N5 exhibited a remarkable piezo-catalytic synthesis rate of 5025 μmol g⁻¹ h⁻¹ under ambient conditions. This efficiency is attributed to H-bonds between CQDs and C3N5, which accelerate PCET in the ORR. The piezoelectric-generated charges, from the dipole field of the C3N5 plane and protons in water, were rapidly transferred to the C rings of CQDs via H-bonds. This process facilitated the adsorption of oxygen onto C2 sites adjacent to carboxyl groups of CQDs, which in turn led to the formation of H2O2 through a rapidly protonated, indirect 2e- pathway. Additionally, a piezo-self-Fenton reaction system was constructed for oxytetracycline-rich wastewater purification, with effectively effects on chemical oxygen demand, antibiotic-resistant bacteria and antibiotic-resistant genes degradation. This study highlights the critical role of H-bond networks for tuning PCET in the ORR and provides a comprehensive understanding for the precise control of catalytic reaction kinetics through molecular structural engineering.

H‐Bonds in Carbon Quantum Dot‐anchored C3N5 to Boost Proton‐Coupled Electron Transfer for Piezoelectric‐Driven Hydrogen Peroxide Synthesis under Ambient Conditions

Tuning proton‐coupled electron transfer (PCET) is a promising strategy to boost the oxygen reduction reaction (ORR) for H2O2 synthesis, but the slow transmission rate of protons and electrons to active sites remains a significant bottleneck. To address this, we developed an H‐bond‐driven PCET process based on carbon quantum dotanchored C3N5 (CQDs‐C3N5) for piezo‐catalytic H2O2 synthesis. CQD‐C3N5 exhibited a remarkable piezo‐catalytic synthesis rate of 5025 μmol g⁻¹ h⁻¹ under ambient conditions. This efficiency is attributed to H‐bonds between CQDs and C3N5, which accelerate PCET in the ORR. The piezoelectric‐generated charges, from the dipole field of the C3N5 plane and protons in water, were rapidly transferred to the C rings of CQDs via H‐bonds. This process facilitated the adsorption of oxygen onto C2 sites adjacent to carboxyl groups of CQDs, which in turn led to the formation of H2O2 through a rapidly protonated, indirect 2e− pathway. Additionally, a piezo‐self‐Fenton reaction system was constructed for oxytetracycline‐rich wastewater purification, with effectively effects on chemical oxygen demand, antibiotic‐resistant bacteria and antibiotic‐resistant genes degradation. This study highlights the critical role of H‐bond networks for tuning PCET in the ORR and provides a comprehensive understanding for the precise control of catalytic reaction kinetics through molecular structural engineering.

Z-scheme heterojunction BiOBr/MIL-100(Fe) visible photocatalytic-permonosulfate degradation of AO7

ABSTRACT Metal–organic frameworks (MOFs) have garnered significant interest in the field of photocatalysis. In this study, Z-scheme heterojunction BM-x composites consisting of bismuth bromide oxide (BiOBr) and iron-based metal–organic backbone (MIL-100(Fe)) were successfully synthesized using ethylene glycol as a solvent. The composites were characterized using various techniques. BM-x exhibit abundant functional groups, large specific surface areas, and narrow band gap energy, thus provide numerous active sites for catalytic reactions and respond well to visible light. Notably, BM-7 displays remarkable catalytic activity in a visible light-activated permonosulfate (PMS) system and achieves a degradation rate of 99.02% over 100 mg/L gold orange II (AO7) within 60 min. The effects of BM-7 and PMS addition, initial AO7 concentration, initial pH, inorganic anions, and humic acid on the degradation system were investigated. The proposed mechanism of the Z-scheme heterojunction in the BM-7 photocatalyst demonstrates effective photoelectron transfer from the BiOBr conduction band to the MIL-100(Fe) valence band, resulting in excellent catalytic activity. Radical burst experiments identified 1O2, h+, and ·O2− as the main active substances. BM-7 has high stability and reusability, with a degradation rate reduction of only 14.48% after three recycles. These findings provide valuable insights into using persulfate combined with visible light.

Heterogeneous Nickel Molybdenum Oxide Nanorods Conjugated Graphitic Carbon Nitride: A Bifunctional Electrocatalyst for Overall Water Splitting.

The pursuit of sustainable energy solutions has driven extensive research into efficient and cost-effective water-splitting techniques. This study introduces a straightforward method employing nickel molybdenum oxide NiMoO4 (NMO) nanorods integrated with graphitic carbon nitride (g-CN) sheets as promising catalysts for water splitting. The integrated coupling between NMO nanorods and g-CN leverages the distinctive properties of both materials to boost robustness as well as effectiveness in catalysis for the oxygen evolution reaction (OER) and hydrogen evolution reaction (HER). We systematically optimized the nanostructure by adjusting the reduction annealing temperature during calcination to improve HER and OER activities. The NMO@g-CN-600 nanostructured catalyst demonstrates exceptional electrochemical HER activity in acidic media, with an overpotential of 148 mV at 10 mA cm-2 current density, which is approximately 2.72 times lower than that of bare NMO and 2.97 times lower than pristine g-CN catalysts. Under alkaline conditions, the NMO@g-CN-600 nanostructured catalyst exhibited superior OER activity with an overpotential of 252 mV to reach a current density of 10 mA cm-2, outperforming bare NMO and pristine g-CN catalysts. Additionally, the nanostructured catalyst demonstrated excellent long-term electrochemical stability with chronoamperometric testing over 50 h in both basic and acidic environments, showing low Tafel slopes for the OER and HER of 97 and 98 mV dec-1, respectively. Various analytical methods confirmed the successful synthesis and structural stability of prepared catalysts. The outstanding electrocatalytic properties of the NMO@g-CN-600 nanostructured catalyst position it as a feasible choice to platinum-group-based catalysts for overall water electrolysis.

Breaking linear scaling relationships in oxygen evolution via dynamic structural regulation of active sites

The universal linear scaling relationships between the adsorption energies of reactive intermediates limit the performance of catalysts in multi-step catalytic reactions. Here, we show how these scaling relationships can be circumvented in electrochemical oxygen evolution reaction by dynamic structural regulation of active sites. We construct a model Ni-Fe2 molecular catalyst via in situ electrochemical activation, which is able to deliver a notable intrinsic oxygen evolution reaction activity. Theoretical calculations and electrokinetic studies reveal that the dynamic evolution of Ni-adsorbate coordination driven by intramolecular proton transfer can effectively alter the electronic structure of the adjacent Fe active centre during the catalytic cycle. This dynamic dual-site cooperation simultaneously lowers the free energy change associated with O–H bond cleavage and O–O bond formation, thereby disrupting the inherent scaling relationship in oxygen evolution reaction. The present study not only advances the development of molecular water oxidation catalysts, but also provides an unconventional paradigm for breaking the linear scaling relationships in multi-intermediates involved catalysis.