Catalysis Research Articles

Stable Tensile-Strained Pt Single Atomic Layer Catalysts on α-MoC for Efficient Alkaline Hydrogen Evolution.

Developing Pt-based core-shell catalysts with ultralow Pt loading, superior performance, and extended durability holds tremendous potential for advancing electrochemical energy storage and conversion technologies. However, current synthetic limitations persist in achieving atomically efficient Pt monolayer deposition on nonprecious metal substrates, hindering the maximization of Pt atomic utilization for cost-effective catalyst design. Here, we demonstrate a galvanic replacement strategy to synthesize tensile-strained platinum single-atom-layer (Pt SAL) on α-MoC substrates. The Pt SAL catalysts enable cooperative catalysis between adjacent Pt sites while maintaining nearly 100% atomic utilization efficiency. For alkaline hydrogen evolution, the Pt SAL/α-MoC catalyst exhibits optimized reaction energetics, reducing activation barriers for water dissociation, hydrogen adsorption, and H2 desorption compared to typical Pt/C. As a result, the Pt SAL catalysts exhibit superior hydrogen evolution reaction (HER) performance, with a mass activity of 1.71 A mgPt-1 at an overpotential of 50 mV, surpassing commercial Pt/C by 6.35-fold and single-atom catalysts by 7.68-fold. Remarkably, the Pt SAL catalysts reveal negligible activity decay after 10,000 cycles, with density functional theory (DFT) calculations attributing this stability to strong Pt-Mo interfacial bonding. In situ Raman spectroscopic studies reveal dynamic interfacial water restructuring that accelerates reaction kinetics. This work establishes a versatile synthesis approach for noble metal SAL catalysts and explores their role in designing high-performance electrocatalysts for heterogeneous catalysis.

Stable Yet Strongly Lewis-Acidic Anions Enabling Cooperative Catalysis with Cationic Transition-Metal Complexes.

Ionic transition-metal complexes play a crucial role as catalysts in organic transformations. Their counteranions often stand aside from the catalytic cycle or occasionally participate in the catalytic cycle as a Brønsted base due to their nucleophilic character. Herein, we developed a stable yet Lewis-acidic anion, BBcat, based on tetrakis(pentafluorophenyl)borate and featuring Lewis-acidic catechol borane moieties and applied it to transition-metal catalysis to recognize Lewis-basic substrates. Upon admixture with Bu4N-BBcat, 31P NMR chemical shift of O═PEt3 significantly lower-shifted, implying the strong Lewis acidity of BBcat despite being an anion. In an Ir complex supported by a bidentate phosphine ligand, BBcat resides in the second coordination sphere as a noncoordinating counteranion. Ir/PHOX-BBcat exhibited an 8.2-fold higher reaction rate than Ir/PHOX-BArF consisting of the non-coordinating anion in the hydrogen isotope exchange of acetophenone derivatives bearing additional Lewis-basic functionalities. The acceleration effect depends on the steric hindrance and basicity of the additional Lewis-basic sites, located at remote positions to the C─H bond to be deuterated. These results clearly indicate that the interaction of BBcat with the Lewis-basic sites plays a crucial role, facilitating cooperative catalysis of the cationic transition-metal center and the counteranion.

Overcoming Challenges in Small‐Ring Transfer: Direct Decarboxylative Hydroalkylation of Alkenes via Iron‐Thiol Catalysis

Cyclopropanes, especially those substituted with trifluoromethyl (CF3) groups, are valuable scaffolds in medicinal chemistry. Their enhanced bioavailability contributes to the widespread presence of this motif in a variety of bioactive compounds. Despite the development of multiple synthetic strategies, a direct method for transferring CF3‐containing small rings from their most abundant carboxylic acid surrogates remains a significant challenge. In this work, we overcome the challenging decarboxylation of CF3‐cyclopropyl and CF3‐cyclobutyl carboxylic acids while leveraging the ligand‐to‐metal charge transfer (LMCT) excited state of photochemically activated iron complexes. The resulting radicals were then engaged in radical addition to alkenes, followed by a timely hydrogen atom transfer (HAT) process mediated by a thiol donor. This efficient iron‐thiol cooperative catalysis enables, for the first time, facile hydroalkylation of alkenes with highly reactive CF3‐containing cyclopropyl and cyclobutyl radicals. Synergistic experimental, spectroscopic, and density functional theory (DFT) studies support the proposed reaction mechanism. Additionally, we employed the radical stabilization energy (RSE) scale, developed using isodesmic equations computed at the DFT level, aiming to provide a better understanding of the reluctant radical decarboxylation of small‐strained cycloalkanes.

Overcoming Challenges in Small-Ring Transfer: Direct Decarboxylative Hydroalkylation of Alkenes via Iron-Thiol Catalysis.

Cyclopropanes, especially those substituted with trifluoromethyl (CF3) groups, are valuable scaffolds in medicinal chemistry. Their enhanced bioavailability contributes to the widespread presence of this motif in a variety of bioactive compounds. Despite the development of multiple synthetic strategies, a direct method for transferring CF3-containing small rings from their most abundant carboxylic acid surrogates remains a significant challenge. In this work, we overcome the challenging decarboxylation of CF3-cyclopropyl and CF3-cyclobutyl carboxylic acids while leveraging the ligand-to-metal charge transfer (LMCT) excited state of photochemically activated iron complexes. The resulting radicals were then engaged in radical addition to alkenes, followed by a timely hydrogen atom transfer (HAT) process mediated by a thiol donor. This efficient iron-thiol cooperative catalysis enables, for the first time, facile hydroalkylation of alkenes with highly reactive CF3-containing cyclopropyl and cyclobutyl radicals. Synergistic experimental, spectroscopic, and density functional theory (DFT) studies support the proposed reaction mechanism. Additionally, we employed the radical stabilization energy (RSE) scale, developed using isodesmic equations computed at the DFT level, aiming to provide a better understanding of the reluctant radical decarboxylation of small-strained cycloalkanes.

Inter‐Site Distance Engineering of Heteronuclear Pd─Cu Atomic Sites Enables High‐Efficiency Cross‐Coupling Reactions Through Atomic‐Scale Locking Pockets

Abstract Precision engineering of intermetallic spacing and electronic synergy in heteronuclear dual‐atom catalysts (DACs) remains a pivotal challenge. Herein, the synthesis of a nitrogen‐doped hollow carbon‐supported Pd─Cu DAC is reported via a polymer‐mediated confinement strategy, achieving sub‐3 Å Pd─Cu spacing. This atomic‐scale proximity, stabilized by 2N‐bridged heteronuclear pairs, supports a charge asymmetry configuration, which enables cooperative catalysis of reactants within active pockets, thereby enhancing the Sonogashira coupling reaction performance. Specifically, electron‐rich Pd activates C─X bonds (X═I, Br, Cl) via optimized electronic structure, while electron‐deficient Cu centers stabilize alkynyl intermediates, effectively suppressing byproducts. The Pd─Cu/NC demonstrates exceptional performance, achieving high selectivity and 94% yield at a turnover frequency of 889 h⁻¹, with ultralow Pd usage (2 ppm). This significantly outperforms long‐distance Pd/Cu single‐atom catalysts (79% yield) and inactive PdCu alloys. Operando spectroscopy and theoretical calculations confirm that fast intermediate transfer between Pd─Cu sites reduces the energy barriers for C─C coupling compared to isolated Pd site systems. The active locking architectures of intimate Pd─Cu sites ensure ligand‐free operation, excellent durability, and broad substrate scope, including bromo‐/chloroarenes, which are challenging in traditional heterogeneous catalysis. This work highlights atomic‐level distance engineering as a key strategy for enhancing site cooperativity efficiency.

Electrocatalytic C─S Cross-Coupling via Engineered Frustrated Lewis Acid-Base Pairs for High-Efficiency Methanesulfonate Synthesis.

The electrochemical synthesis of sulfonyl compounds under mild conditions remains a significant challenge due to the reliance on harsh reagents, high energy consumption, and low selectivity in conventional methods. Herein, we report a novel strategy for efficient C─S bond formation through in situ modulation of frustrated Lewis acid-base pairs within a copper-based metal-organic framework (CuBDC-XN). By precisely engineering electron-deficient Cu Lewis acid sites and electron-rich XN-functionalized Lewis base sites, this bifunctional catalyst enables the synergistic co-reduction of SO3 2- and CO2 into methanesulfonate (MS) at ambient conditions with a Faradaic efficiency of 13.77% (-0.78V versus RHE). Mechanistic studies reveal that the frustrated Lewis pairs selectively stabilize key intermediates (*CHO and SO3 2-) via electrostatic interactions, facilitating nucleophilic attack and C─S coupling with a reduced energy barrier (0.48eV). In situ spectroscopic analyses and DFT calculations further elucidate the dynamic adsorption-configuration regulation and intermediate evolution pathway. This work not only establishes a molecular-level understanding of cooperative Lewis acid-base catalysis but also provides a universal design principle for the sustainable electrosynthesis of value-added organosulfur compounds.

Regulation of Ni Single-Atom/Nanoparticle Cooperative Catalytic Systems by P Heteroatom Asymmetric Coordination for Efficient Electrocatalytic CO2 Reduction.

Earth-abundant transition-metal-based single-atom catalysts and nanoparticulate catalysts exhibit relatively high performance for the electrocatalytic CO2 reduction reaction (eCO2RR). However, the localized orbital structures of active sites of single-atom catalysts make it difficult to effectively couple key intermediates, thereby limiting their catalytic performance. Nanoparticulate catalysts are prone to aggregation during the eCO2RR, leading to an unwanted hydrogen evolution reaction. In response to these problems, a porous carbon catalyst with Ni─N─P ternary co-doping through a two-step pyrolysis process is prepared. Ni nanoparticles (NPs) are encapsulated in the carbon support and atomically dispersed Ni single atoms (SAs) are anchored to the carbon support surface. The internal Ni─NPs provide electrons for the surface Ni─SAs, thereby helping enhance the electron-transfer efficiency. The doping element P not only tailors the sizes of Ni─NPs, suppressing their hydrogen evolution activity but also forms the asymmetric NiN3P─SA active sites, enhancing the coupling strength between the catalyst and adsorbed intermediates. Given the unique structural features, this porous Ni─N─P ternary co-doped coal-based catalyst achieves increased CO selectivity (95%), current density (227.4 mA cm-2) and stability (120 h).

Theoretical Explanation of Diatomic Synergies and Repulsion Interactions between ORR/OER Catalytic Intermediates.

Oxygen reduction reactions (ORR) and oxygen evolution reactions (OER) are pivotal in energy conversion. Herein, first-principles calculations are employed to explore cooperative catalysis's influence on catalysts with doping and adsorption configurations. Specifically, doped and adsorbed metal atoms are explored on MXene, analyze bimetallic system's electronic properties via density of states, and investigate catalytic activity in homonuclear and heteronuclear diatomic cooperative reactions. It is found that heteronuclear diatomic cooperation substantially enhances catalyst activity, unveiling high-efficacy catalysts like Ni&/Co*OOH (ηORR/OER/Bi = 0.29/0.37/0.66 V) and Ni&/Co*O (ηORR/OER/Bi = 0.40/0.16/0.56 V). Such ultra-high catalytic activity is primarily attributed to the repulsive interactions between catalytic intermediates at neighboring active sites, which modulate the charge distribution at the target sites during the catalytic process, as well as the density of atomic orbital centers of the catalytic atoms. The findings offer a potential explanation for the discrepancies observed between theoretical calculations and experimental results.

Bioinspired Chiral Peptide-Phosphonium Salt Catalysis: From Enzymes to Cationic Small-Molecule Enzyme Mimics.

ConspectusEnzymes exemplify nature's catalytic mastery through precise stereochemical control and remarkable rate enhancements, yet their synthetic application remains limited by inherent vulnerabilities: thermal instability, narrow substrate tolerance, and complex engineering requirements. These challenges drive our pursuit of modular organocatalysts that emulate enzymatic cooperativity while combining ease of synthesis, versatility, and high tunability, termed "bioinspired organic small-molecule enzymes".In this Account, we detail the creation of peptide-phosphonium salt (PPS) catalysts that marry conformationally ordered peptide scaffolds with phase-transfer-active phosphonium cations. This design strategically combines (1) programmable peptide secondary structures (α-helices/β-sheets) for spatial control of hydrogen-bonding networks, (2) tunable phosphonium centers (electronic/steric modulation via aryl/alkyl substituents) for electrostatic activation, and (3) modular architecture enabling three-dimensional optimization (peptide sequences, cation substituents, and counterions). Such integration permits systematic enhancement of stereoselectivity and catalytic efficiency across diverse reaction manifolds under ambient conditions.The PPS platform has revolutionized challenging asymmetric annulation reactions. Our initial breakthrough in aza-Darzens reactions (formal [2 + 1]) established a general method for synthesizing sterically hindered enantioenriched aziridines, overcoming long-standing stereochemical challenges through synergistic substrate preorganization by peptide hydrogen bonding and charge stabilization by phosphonium ion-pairing interactions. Subsequent expansion to a variety of cycloadditions, including [2 + 2], [3 + 2], [4 + 2], and formal [4 + 3]/[5 + 1]/[5 + 2]/[6 + 1]/[6 + 2], etc. delivered structurally diverse chiral N-heterocycles, while pioneering the first catalytic asymmetric Atherton-Todd reaction enabled the stereodivergent synthesis of P-chiral compounds, significantly expanding the toolbox for phosphorus stereochemistry. Beyond single-molecule catalysis, PPS catalysts exhibit excellent adaptability in relay and cooperative catalysis systems. A bifunctional PPS/Lewis base relay catalysis system achieved efficient axial chirality induction in biaryl phosphates, while metal-cooperative platforms enabled stereocontrolled synthesis of strained medium rings, including seven- to nine-membered systems, through synergistic weak-bonding and metal catalysis. These advances underscore PPS catalysts as versatile platforms surpassing enzymatic systems in construction of structurally diverse chiral molecules.This Account not only summarizes our progress in PPS catalyst development and applications but also highlights the mechanistic insights, providing design principles for next-generation enzyme mimics. By emulating nature's strategy, we envision expanding PPS catalysis to address unmet challenges in asymmetric synthesis, from enzymatic-level stereochemical editing to the sustainable manufacturing of chiral substances.

Convergent synthesis of steviol glycosides rebaudioside a and M.

Convergent synthesis of steviol glycosides rebaudioside a and M.

Dynamic Hydrogen Bonding Tuned Enantioselectivity Control in Cobaloxime-Chiral Amine Cooperative Catalysis.

Cobaloxime is a versatile 3d-metal catalyst for dehydrogenative radical coupling reactions. Prior mechanistic studies of cobaloxime catalysis have revealed that cobaloxime(II)-catalyzed hydrogen atom transfer (HAT) process can control the site-selectivity and chemoselectivity of radical transformation. However, the relevance of HAT to the enantioselectivity is seldom reported. Herein, our density functional theory studies of the cobaloxime-chiral amine co-catalyzed enantioselective coupling of the enamine radical cation with alkene proved that it is the HAT step that determines the enantioselectivity, instead of the previously proposed radical addition. Because the metal-alkene-coupled (MAC) radical addition is a reversible process while the followed by HAT is the rate-determining step. Moreover, computational studies suggest that the dynamically changing hydrogen bonding between the radical cation and cobaloxime plays a significant role in harnessing the reactivity and tuning the enantiocontrol. The intra- and inter-molecular hydrogen bonding between the iminium and the cobaloxime fragments contributes to the lower energy barrier of MAC radical addition. Structural analysis and quantitative steric-electronic effect dissection jointly unveiled that the stronger intermolecular hydrogen bonding between the aminium and the cobaloxime fragments is the dominant factor that stabilizes the (R)-HAT transition state and guarantees high enantioselectivity.

Dynamic Hydrogen Bonding Tuned Enantioselectivity Control in Cobaloxime‐Chiral Amine Cooperative Catalysis

Abstract Cobaloxime is a versatile 3d‐metal catalyst for dehydrogenative radical coupling reactions. Prior mechanistic studies of cobaloxime catalysis have revealed that cobaloxime(II)‐catalyzed hydrogen atom transfer (HAT) process can control the site‐selectivity and chemoselectivity of radical transformation. However, the relevance of HAT to the enantioselectivity is seldom reported. Herein, our density functional theory studies of the cobaloxime‐chiral amine co‐catalyzed enantioselective coupling of the enamine radical cation with alkene proved that it is the HAT step that determines the enantioselectivity, instead of the previously proposed radical addition. Because the metal–alkene‐coupled (MAC) radical addition is a reversible process while the followed by HAT is the rate‐determining step. Moreover, computational studies suggest that the dynamically changing hydrogen bonding between the radical cation and cobaloxime plays a significant role in harnessing the reactivity and tuning the enantiocontrol. The intra‐ and inter‐molecular hydrogen bonding between the iminium and the cobaloxime fragments contributes to the lower energy barrier of MAC radical addition. Structural analysis and quantitative steric‐electronic effect dissection jointly unveiled that the stronger intermolecular hydrogen bonding between the aminium and the cobaloxime fragments is the dominant factor that stabilizes the (R)‐HAT transition state and guarantees high enantioselectivity.

Supramolecularly Confined Catalysis in Polyphthalocyanine‐Crown‐Ether Frameworks Boosts Sulfur Redox Kinetics

Abstract Metal phthalocyanines are considered as potent catalysts in lithium–sulfur (Li–S) chemistry. However, their adsorption capability is deficient to inhibit polysulfides from shuttling, which in turn retards the S‐redox reaction in the cathode. Here we report flexible, two‐dimensional (2D) polyphthalocyanine‐crown‐ether (PPc‐CE) frameworks that provide a supramolecularly confined space created with the single‐atom catalytic nickel phthalocyanine nodes and crown‐ether linkers as Li host. Electrochemical and theoretical analyses reveal that a cooperative redox catalysis with the enhanced lithiophilicity of PPc‐CE‐coated carbon nanotubes (PPc‐CE/CNTs) boosts Li–S redox kinetics and, meanwhile, suppresses the growth of Li dendrites for the long term. A Li||S cell employing PPc‐CE/CNT catalysts delivers a high discharge capacity of 1,363 mAh g−1 at 0.1C and still retains a specific capacity of ∼700 mAh g−1 over 500 cycles at 1C. Our work provides insights into the molecular design of redox catalysts for Li–S batteries based on 2D polymers.

Supramolecularly Confined Catalysis in Polyphthalocyanine-Crown-Ether Frameworks Boosts Sulfur Redox Kinetics.

Metal phthalocyanines are considered as potent catalysts in lithium-sulfur (Li-S) chemistry. However, their adsorption capability is deficient to inhibit polysulfides from shuttling, which in turn retards the S-redox reaction in the cathode. Here we report flexible, two-dimensional (2D) polyphthalocyanine-crown-ether (PPc-CE) frameworks that provide a supramolecularly confined space created with the single-atom catalytic nickel phthalocyanine nodes and crown-ether linkers as Li host. Electrochemical and theoretical analyses reveal that a cooperative redox catalysis with the enhanced lithiophilicity of PPc-CE-coated carbon nanotubes (PPc-CE/CNTs) boosts Li-S redox kinetics and, meanwhile, suppresses the growth of Li dendrites for the long term. A Li||S cell employing PPc-CE/CNT catalysts delivers a high discharge capacity of 1,363 mAh g-1 at 0.1C and still retains a specific capacity of ∼700 mAh g-1 over 500 cycles at 1C. Our work provides insights into the molecular design of redox catalysts for Li-S batteries based on 2D polymers.

Mn(I)‐NNSe Pincer Complex Catalyzed Regioselective Synthesis of Bisindolylmethanes under Base and Solvent‐Free Conditions

Abstract Here, we present a catalytic, regioselective synthesis of bisindolylmethanes through the reaction of indoles and benzyl alcohol derivatives mediated by metal‐ligand cooperative catalysis. The reaction is catalyzed by an earth‐abundant manganese‐NNSe pincer complex without the need for base, solvent, additives, or hydrogen acceptors yielding water and dihydrogen as environmentally friendly by‐products. Notably, C‐3 and N‐alkylation of indole, commonly observed in similar reactions were not detected. Mechanistic studies suggest that metal‐ligand cooperative catalysis by the Mn(I)‐NNSe pincer complex initiates the conversion of benzyl alcohol to benzaldehyde through dihydrogen elimination, which subsequently facilitates the synthesis of bisindolylmethane derivatives. To highlight the practical utility of this method, a wide range of substrates can be activated with low catalyst loading under mild reaction conditions.

Cooperative Photometallobiocatalysis: Nonheme Fe Enzyme-Catalyzed Enantioconvergent Radical Decarboxylative Azidation, Thiocyanation, and Isocyanation of Redox-Active Esters.

Cooperative catalysis with an enzyme and a small-molecule photocatalyst has recently emerged as a potentially general activation mode to advance novel biocatalytic reactions with synthetic utility. Herein, we report cooperative photobiocatalysis involving an engineered nonheme Fe enzyme and a tailored photoredox catalyst to achieve enantioconvergent decarboxylative azidation, thiocyanation, and isocyanation of redox-active esters via a radical mechanism. We repurposed and further evolved metapyrocatechase (MPC), a nonheme Fe extradiol dioxygenase not previously studied in new-to-nature biocatalysis, for the enantioselective C─N3, C─SCN, and C─NCO bond formation via an enzymatic Fe─X intermediate (X═N3, NCS, and NCO). A range of primary, secondary, and tertiary alkyl radical precursors were effectively converted by our engineered MPC, allowing the syntheses of organic azides, thiocyanates, and isocyanates with good to excellent enantiocontrol. Further derivatization of these products furnished valuable compounds including enantioenriched amines, triazoles, ureas, and SCF3-containing products. DFT and MD simulations shed light on the mechanism as well as the binding poses of the alkyl radical intermediate in the enzyme active site and the π-facial selectivity in the enantiodetermining radical rebound. Overall, cooperative photometallobiocatalysis with nonheme Fe enzymes provides a means to develop challenging asymmetric radical transformations eluding small-molecule catalysis.

NHC/Pd Synergistically Catalyzed Direct Aerobic Oxidative Allylic Esterification of Aldehydes.

N-Heterocyclic carbene (NHC)-mediated aerobic oxidation of aldehydes has gained interest in recent years. However, its application in NHC/Pd synergistic catalysis has been unexplored. We have developed a strategy to synthesize allylic esters directly from aldehydes and Morita-Baylis-Hillman (MBH) carbonates using NHC/Pd synergistic (cooperative) catalysis under aerobic conditions. This transformation gives access to the selective formation of multifunctionalized E-alkenes by β-attack on the MBH carbonates. This catalytic system also allows the use of water as a cosolvent and air as the sole green oxidant.

Review on Cooperative Catalysis for Room-Temperature Sodium-Sulfur Batteries.

The low cost and high energy density characteristics of room-temperature sodium-sulfur (RT Na-S) batteries remarkably promote the development of sustainable large-scale energy-storage systems. However, there are serious problems with the shuttle effect and slow conversion kinetics caused by polysulfide dissolution in RT Na-S batteries, which can lead to decreased coulombic efficiency, rapid capacity degradation, and poor rate performance, hindering the practical application of RT Na-S batteries. Recently, numerous multimodal approaches have been attempted to address these issues, thereby promoting cycling stability and raising the energy density of RT Na-S batteries to a higher level. However, there is still a lack of a comprehensive and systematic summary of catalyst design based on the cooperative catalysis principle. In this review, the application advantages, operation mechanisms, and main challenges of RT Na-S batteries are first introduced. After that, the latest progress based on cooperative catalysts is elaborately summarized, exploring the corresponding work mechanisms and design principles of RT Na-S batteries. Finally, a summary of future research directions for developing high-performance RT Na-S batteries is presented.

Synergistic solvent-catalyst paradigm for sustainable aerobic allylic C–H functionalization

Abstract Achieving sustainable catalytic transformations requires synergistic optimization of solvent systems, catalytic motifs and energy inputs. Herein, we report a synergistic Pd/hydroquinone catalytic system that enables aerobic allylic C–H functions under ambient conditions (room temperature to 50°C, air) with high turnover frequency (TOF), using ethanol/water as a green medium. This strategy achieves unparalleled synthetic efficiency and demonstrates remarkable versatility across two pivotal transformations (alkylation and amination) involving over 90 products (up to 99% yield). It also delivers exceptional stereocontrol (up to 93% ee for quaternary stereocenters) and enables advanced allylic transformations within a green framework through additional synergistic catalysis. By integrating solvent engineering with cooperative catalysis, we have developed a scalable platform for the synthesis of allylic functionalized moelcules with pharmaceutical interests, demonstrating how molecule-level innovation can drive sustainable industrial transformation.

Single-Crystal Metal-Organic and Covalent Organic Framework Hybrids Enable Efficient Photoelectrochemical CO2 Reduction to Ethanol.

Multicarbon alcohols produced through photochemical and electrochemical CO2 reduction reactions (CO2RR) are promising alternatives to fossil fuels; however, their selectivity and efficiency remain low due to the high energy barrier for C-C coupling and the competition from hydrocarbon production. Here, we present a strategy to enhance ethanol efficiency and selectivity via cooperative catalysis in porous structures for photoelectrochemical (PEC) CO2RR. Using a coordination-templated strategy, we synthesized single crystals of MOF-COF (MOCOF) hybrids with metalloporphyrins, with their structures determined by single-crystal 3D electron diffraction. The porous frameworks featuring adjacent confined metalloporphyrins efficiently capture and cooperatively activate CO2, achieving outstanding PEC CO2-to-ethanol conversion. Particularly, the Pt-MOCOF delivers a Faradaic efficiency (FE) of 83.5% at -1.0 V with 91.7% carbon selectivity, surpassing state-of-the-art COF or MOF catalysts and ranking it among the top-performing catalysts. The catalyst system displays remarkable stability, maintaining 95% of its activity after 100 h of continuous operation. Experiments and theoretical calculations revealed that the cooperative catalyst enriches and stabilizes intermediates in the channels, guiding the reaction pathway toward ethanol production.