High Turnover Frequency Research Articles

Benzimidazole-based covalent organic framework embedding single-atom Pt sites for visible-light-driven photocatalytic hydrogen evolution

Visible-light-driven photocatalytic hydrogen evolution reaction (HER) over a semiconductor provides an effective avenue to produce renewable clean energy and alleviate energy and environmental crises. However, the HER efficiency is still limited by the sluggish electron transfer process. Herein, a highly active covalent organic framework (COF) was constructed from the unusual benzimidazole monomer in a microwave-assisted solvothermal pathway. With single-atom Pt sites as cocatalyst, the catalyst exhibited an HER rate up to 115 mmol g–1 h–1 and a high turnover frequency of 4475.1 h–1 under visible-light irradiation. The above performance relied on the combination of benzimidazole moieties and COF framework, which, on the one hand, stabilized photogenerated electrons to prolong the electron lifetime, and on the other hand provided a strong host-guest interaction that resulted in the creation of single-atom Pt sites and the acceleration of the electron-transfer to the active sites for proton reduction. This work demonstrates the perspective of electron stabilization and interfacial charge transfer avenue construction in the HER process, which can be reached by a molecular-level design of COF-based organic semiconductors by using structural and functional diverse asymmetric building blocks.

Hierarchical Co3O4/SAPO-34 supported PtCo bimetallic nanoparticles as highly efficient catalyst for hydrogen generation from ammonia borane hydrolysis

Hierarchical Co3O4/SAPO-34 supported PtCo bimetallic nanoparticles (NPs) with uniform dispersion and narrow size-distribution were prepared for the hydrolysis of AB to produce hydrogen. Strategies including the sequential impregnation of cobalt and platinum precursors followed by partial reduction were employed to anchor Pt NPs. Befitting from the interfacial interaction between Co and Co3O4 NPs, the intermetallic synergistic effect of PtCo NPs and the synergistic interaction between Co NPs and SAPO-34 zeolite, the prepared Pt@Co/Co3O4/SP-10(400,2) catalyst exhibited outstanding catalytic activity with a high turnover frequency (TOF) value of 314 molH2(molPt·min)-1 at 303 K. In addition, the flake-assemble hierarchical structure of SAPO-34 played an important role in improving the dispersion of metal NPs and the mass transfer rate between reactants and active sites.

Fast and Durable Dehydrogenation of Formic Acid over Pd–Cr(OH)3 Nanoclusters Immobilized on Amino-Modified Reduced Graphene Oxide

Formic acid, attractive as a renewable and safe liquid organic hydrogen carrier (LOHC), can be obtained by biomass conversion and CO2 hydrogenation with green hydrogen. The efficient and durable catalysts for formic acid dehydrogenation (FAD) are beneficial in the industry. Herein, Cr(OH)3-promoted Pd nanoclusters (NCs) (i.e., 1.6 nm) immobilized on amino-modified reduced graphene oxide (NH2-rGO) were successfully prepared through a simple wet-chemical approach. The obtained Pd–Cr(OH)3/NH2-rGO catalyst exhibits excellent catalytic activity and 100% hydrogen selectivity for CO-free FAD, giving a high turnover frequency of 2519.5 h–1 at 323 K, outperforming most reported Pd-based heterogeneous catalysts. Especially, the catalyst possesses robust durability toward FAD with no significant decline in activity and aggregation of metal NCs even after 10 cycles. The superior performance of the catalyst may be ascribed to the well-distributed Pd–Cr(OH)3 NCs, the strong electronic coupling of Pd with Cr(OH)3, the synergetic interaction of Pd–Cr(OH)3 with NH2-rGO, and the promotion effect of amino group. The reaction mechanism of FAD was explored based on the isotope experiments. This work provides insights into designing an effective and durable heterogeneous catalyst for dehydrogenation of LOHC.

Cu-doped Heterointerfaced Ru/RuSe2 nanosheets with optimized H and H2 O adsorption boost hydrogen evolution catalysis.

Ruthenium chalcogenide is a highly promising catalytic system as a Pt alternative for hydrogen evolution reaction (HER). However, well-studied ruthenium selenide (RuSe2 ) still exhibits sluggish HER kinetics in alkaline media due to the inappropriate adsorption strength of H and H2 O. Herein, w e report a new design of Cu-doped Ru/RuSe2 heterogeneous nanosheets (NSs) with optimized H and H2 O adsorption strength for highly efficient HER catalysis in alkaline media. Theoretical calculations reveal that the superior HER performance is attributed to a synergistic effect of the unique heterogeneous interface structure and Cu doping, which not only optimizes the electronic structure with a suitable d-band center to suppress proton overbinding but also alleviates the energy barrier with enhanced H2 O adsorption. As a result, Cu-doped heterogeneous Ru/RuSe2 NSs exhibit a small overpotential of 23mV at 10mA cm-2 , a low Tafel slope of 58.5mV dec-1 and a high turnover frequency (TOF) value of 0.88 s-1 at 100mV for HER in alkaline media, which is among the best catalysts in noble metal-based electrocatalysts toward HER. The present Cu-doped Ru/RuSe2 NSs interface catalyst is very stable for HER by showing no activity decay after 5000-cycle potential sweeps. This work heralds that heterogeneous interface modulation opens up a new strategy for the designing of more efficient electrocatalysts. This article is protected by copyright. All rights reserved.

Enhanced adsorption with hydroxymethyl and aldehyde over the heterophase interface for efficient biomass electrooxidation

Co3O4 has displayed promising ability for 5-hydroxymethylfurfural (HMF) electrooxidation reaction (HMFOR), which is an efficient way to produce high-value chemicals. However, its poor intrinsic ability has seriously limited its electrochemical performance. The introduction of foreign components into Co3O4via heterophase interfacing is an efficient strategy to enhance its intrinsic activity. Herein, we have modified Co3O4 through the fabrication of the heterophase interface between Cu-doped Co3O4 (Cu−Co3O4) and CuO (Cu−Co3O4/CuO). With the introduction of Cu species, the electronic structure of the electrocatalyst has been well-modulated, whose electrons were preferentially transformed from Co to Cu atoms, suggesting a strong electron interaction. The electrochemical results suggest that Cu−Co3O4/CuO exhibited a lower overpotential, faster reaction kinetics, and higher turnover frequency than Cu−Co3O4 and pure Co3O4. Experimental results and theoretical calculations demonstrate that the fabrication of the heterophase interface could have strong adsorption toward HMF owing to the enhanced interaction with the aldehyde and hydroxymethyl groups. Furthermore, Cu−Co3O4/CuO possessed a relatively poor reliance on the furan ring for HMF adsorption but accelerated the oxidation of the aldehyde group. This work provides a significant reference for the development of efficient HMFOR electrocatalysts.

Pd Sulfidation‐Induced 1T‐Phase Tuning in Monolayer MoS2 for Hydrogen Evolution Reaction

AbstractFor single‐atom‐layer hydrogen evolution reaction catalysts, enrichment of the 1T‐phase in monolayer molybdenum disulfide is important to achieve ideal metal utilization efficiency and exposure of active surface atoms. Herein, it is discovered that the 1T‐phase degree in monolayer MoS2 can be enhanced through sulfidation of the Pd species deposited on MoS2 (PdxSy/1T‐MoS2). Raman and X‐ray photoelectron spectroscopy reveal that the sulfidation‐assisted phase transition results in considerably greater proportions of 1T‐phase fraction (up to 86%) without using alkali‐metal‐based approaches. Observations of S‐atom displacement/translation at the atomic level contribute to the understanding of the phase transformation of MoS2. The maximized surface atom activation and metal utilization efficiency in PdxSy/1T‐MoS2 lead to unprecedentedly high mass activity (−3444 A mgPd−1) and turnover frequency (1892 s−1), three orders of magnitude higher than those of commercial Pt/C 10 wt% (3.6 A mgPt−1 and 3.6 s−1). The sulfidation‐assisted 1T‐phase enrichment has major implications for the designs of efficient electrocatalysts through MoS2 phase engineering.

Longitudinally Grafting of Graphene with Iron Phthalocyanine-based Porous Organic Polymer to Boost Oxygen Electroreduction.

Iron phthalocyanine-based polymers (PFePc) are attractive noble-metal-free candidates for catalyzing oxygen reduction reaction (ORR). However, the low site-exposure degree and poor electrical conductivity of bulk PFePc restricted their practical applications. Herein, laminar PFePc nanosheets covalently and longitudinally linked to graphene (3D-G-PFePc) was prepared. Such structural engineering qualifies 3D-G-PFePc with high site utilization and rapid mass transfer. Thence, 3D-G-PFePc demonstrates efficient ORR performance with a high specific activity of 69.31 μA cm-2, a high mass activity of 81.88 A g-1, and a high turnover frequency of 0.93 e s-1 site-1 at 0.90 V vs reversible hydrogen electrode in O2-saturated 0.1 M KOH, outperforming the lamellar PFePc wrapped graphene counterpart. Systematic electrochemical analyses integrating variable-frequency square wave voltammetry and in-situ scanning electrochemical microscopy further underline the rapid kinetics of 3D-G-PFePc towards ORR.

Longitudinally Grafting of Graphene with Iron Phthalocyanine‐based Porous Organic Polymer to Boost Oxygen Electroreduction

AbstractIron phthalocyanine‐based polymers (PFePc) are attractive noble‐metal‐free candidates for catalyzing oxygen reduction reaction (ORR). However, the low site‐exposure degree and poor electrical conductivity of bulk PFePc restricted their practical applications. Herein, laminar PFePc nanosheets covalently and longitudinally linked to graphene (3D‐G‐PFePc) was prepared. Such structural engineering qualifies 3D‐G‐PFePc with high site utilization and rapid mass transfer. Thence, 3D‐G‐PFePc demonstrates efficient ORR performance with a high specific activity of 69.31 μA cm−2, a high mass activity of 81.88 A g−1, and a high turnover frequency of 0.93 e s−1 site−1 at 0.90 V vs. reversible hydrogen electrode in O2‐saturated 0.1 M KOH, outperforming the lamellar PFePc wrapped graphene counterpart. Systematic electrochemical analyses integrating variable‐frequency square wave voltammetry and in situ scanning electrochemical microscopy further underline the rapid kinetics of 3D‐G‐PFePc towards ORR.

Enhanced Surface Charge Localization Over Nitrogen-Doped In2O3 for CO2 Hydrogenation to Methanol with Improved Stability

Indium oxide (In2O3) is active and promising for selective hydrogenation of CO2 to methanol. However, it suffers from over-reduction at elevated temperatures, causing deactivation. Herein, a nitrogen-doped In2O3 (N–In2O3) catalyst was prepared using a plasma-intensified nitrogen-doping technology. It is confirmed that nitrogen doping is effective for the stabilization of In2O3. The doped nitrogen enhances the surface charge localization, which inhibits the over-reduction on the oxide surface and limits the generation of excessive surface oxygen vacancies. The doped nitrogen also serves as the active site, synergistically with surface oxygen vacancy, which leads to an enhanced dissociation of CO2 to adsorbed CO* intermediates. The electron-rich nitrogen causes a strong adsorption of CO on N–In2O3 and inhibits the formation of free CO. A significantly improved methanol selectivity with a higher turnover frequency (TOF) is thus achieved on N–In2O3, compared to the un-doped In2O3. For example, at 21,000 cm3 h–1 gcat–1, 300 °C, and 5 MPa, the TOF of N–In2O3 reaches 37.0 h–1 with methanol selectivity of 75.1%, while the TOF of the un-doped In2O3 is only 16.0 h–1 with methanol selectivity of 62.3%. Different from pristine In2O3, N–In2O3 takes the CO hydrogenation route for CO2 hydrogenation to methanol. This explains the reason why the N–In2O3 catalyst possesses improved selectivity for CO2 hydrogenation to methanol.

Microwave-Assisted Synthesis of Highly Active Single-Atom Fe/N/C Catalysts for High-Performance Aqueous and Flexible All-Solid-State Zn-Air Batteries.

The development of low-cost single-atom electrocatalysts for oxygen reduction reaction (ORR) is highly desired but remains a grand challenge. Superior to the conventional techniques, a microwave-assisted strategy is reported for rapid production of high-quality Fe/N/C single-atom catalysts (SACs) with profoundly enhanced reaction rate and remarkably reduced energy consumption. The as-synthesized catalysts exhibit an excellent ORR performance with a positive half-wave potential up to 0.90V, a high turnover frequency of 0.76 s-1 , as well as a satisfied stability with a lost half-wave potential of just 27mV over 9000 cycles (much better than that of Pt/C with 107mV lost) and good methanol resistance. The open-circuit voltages of as-constructed aqueous and flexible all-solid-state Zn-air batteries (ZABs) are 1.56 and 1.52V, respectively, higher than those of 20% Pt/C-based ones (i.e., 1.43 and 1.38V, respectively). Impressively, they afford a peak power density of 235mW cm-2 , which exceeds that of Pt/C (i.e., 186mW cm-2 ), and is comparable to the best ones of Fe/N/C-based ZABs ever reported.

Enhanced CO Functionality on Carbon Papers Ensures Lowering Nucleation Delay of ALD for Ru towards Unprecedented Alkaline HER Activity.

The success in lowering the nucleation delay for Atomic Layer Deposition (ALD) of Ru on carbon surfaces is mitigated by constructive pretreatments resulting enhancement of CO functionality. Treatment of the carbon papers (CP) allowed Ru species deposition for minimum number of ALD cycles (25 cycles) with good conformality. The development of electrocatalysts from single atoms to nanoparticles (NPs) on conductive supports with low metal loadings, thus improving performance, is essential in electrocatalysis. For alkaline hydrogen evolution reaction, ALD decorated CPs with Ru exhibit low onset potentials of ≈4.7mV versus reversable hydrogen electrode (RHE) (at 10mAcm-2 ) and a high turnover frequency of 1.92 H2 s-1 at 30mV versus RHE. The Ru decorated CPs show comparable to higher catalytic activity than of Platinum (Pt) decorated CP also developed by ALD. The current representation of unfamiliar catalytic activities of Ru active centers developed by ALD, pave a bright and sustainable path for energy conversion reactions.

Heterostructure and phase engineering synergistically activated highly efficient alkaline hydrogen evolution in Mo2C/MoS2-rGO hybrids

Heterostructure and phase engineering are effective method to tune the electronic structure of MoS2, which can activate and boost its intrinsic catalytic activity. Herein, the theoretical calculations reveal that the free energy of H∗ adsorption (ΔGH∗) for Mo2C (−0.65 eV) is lower than MoS2 (2.05 eV), which is favorable for hydrogen adsorption. Inspired by the theoretical predictions, we develop a facile strategy to prepare nanostructured Mo2C/MoS2 dispersed on reduced graphene oxide (rGO) via a hydrothermal preparation and carburization reaction. Since the Mo2C/MoS2-rGO nanostructures with great deal of both MoS2 and Mo2C edges by heterostructure and phase engineering, which can induce massive active sites for HER on the surface of rGO, the intimate interfacial coupling effect between Mo2C and MoS2 can effectively improve the charge transfer rate. The Mo2C/MoS2-rGO catalyst exhibits exceptional HER properties, delivering a high turnover frequency (TOF) of 0.209 s−1 at an overpotential of 200 mV in 0.1 M KOH. This work may open a new window for designing NPM electrocatalysts with highly efficient HER property based on earth-abundant materials.

Promoting propane dehydrogenation over PtFe bimetallic catalysts by optimizing the state of Fe species

Optimizing the structure of Pt-based bimetallic catalysts is of utmost importance toward improving the propane dehydrogenation performance. It is challenging to precisely synthesize uniform PtFe alloy nanoparticles without excess unalloyed Fe species on the support as these Fe species lead to low propylene selectivity, coke deposition, and poor stability. Herein, we report an effective strategy to optimize the structure of PtFe bimetallic catalysts with minimal coke and high turnover frequency (8.2 s−1). For the optimized catalyst, 1Pt3Fe@S-1, most Fe species is in the framework of the zeolite S-1, which significantly suppresses the formation of coke. In addition, the extra-framework Fe and Pt species encapsulated in the channel of zeolite form uniform PtFe alloy nanoparticles, which significantly improves the C3H6 selectivity, catalytic stability, and recycling performance. These findings provide insights into the structure-performance relationship of PtFe bimetallic catalysts and shall be beneficial to future design and optimization of similar catalytic materials.

Hydrothermally synthesized MoSe2/ZnO composite with enhanced hydrogen evolution reaction

Efficient hydrogen evolution reaction is going to be the primary sustainable source of energy in the future. To achieve this, non-metal catalysts are required to replace the cutting-edge catalysts like platinum with affordable earth-abundant and long-lasting electrocatalysts. For efficient hydrogen evolution reaction, 1T phase of MoSe2 nanosheets has been found to display superior catalytic properties due to exposed edges. Unfortunately, the catalytic activity of such nanosheets for hydrogen evolution reaction is limited due to inevitable agglomeration and stacking of the liquid exfoliated nanosheets and their intrinsic lower conductivity. In order to mitigate these issues composites with other low dimensional materials have shown enhanced catalytic performance. Here, in this study, we describe such a composite using MoSe2 and ZnO. Out of various compositions, the one with a MoSe2 and ZnO with weight ratio 2:1 outperformed in terms of enhanced electrocatalytic activity. This sample displayed lower overpotential (0.25 V at 10 mA/cm2), and onset potential (0.11 V at 1 mA/cm2). As a result, the reaction kinetics are consistent with the Volmer-Heyrovsky mechanism, as indicated by the lower Tafel slope of 87 mV/dec. In addition, optimized composite also exhibit larger effective surface area, higher turnover frequency (0.81 s−1) and lower charge transfer contact resistance. Thus heterojunction between TMDC's and semiconductor oxides may create new pathways for enhancing the HER activity.

Oxygen vacancy regulated valence states of Pt on rutile TiO2 promote catalytic oxidation of HCHO

Anatase-TiO2-supported Pt (Pt/TiO2(A)) is a well-known supported catalyst for catalyzing the oxidation of formaldehyde (HCHO). However, rutile TiO2 (TiO2(R)) has not been widely utilized for this reaction due to its inferior performance. In this study, we have developed a novel approach involving NaBH4-induced oxygen vacancy manipulation to regulate the valence states of Pt on TiO2(R). By employing a large excess of NaBH4 (nNaBH4/nPt = 2000), we were able to generate an extraordinary concentration of oxygen defects and electron-rich sites on the surface of TiO2(R), resulting in the concentration of Pt0 on Pt/TiO2(R)− 2000 exceeding that on Pt/TiO2(A)− 2000. The newly synthesized Pt/TiO2(R)− 2000 catalyst exhibited a remarkably high turnover frequency (TOF) of 160.2 h−1, which is approximately five times that of Pt/TiO2(R)− 20. The discrepancy in the reaction mechanisms between rutile and anatase was identified as the critical factor underlying the vastly different performances observed.

A novel peroxymonosulfate activation process by single-atom iron catalyst from waste biomass for efficient singlet oxygen-mediated degradation of organic pollutants

Single-atom dispersed catalysts (SACs) have gained considerable attention in organic contaminants remediation due to their superior reactivity and stability. However, the complex and costly synthesis processes limit their practical applications in environmental protection. Herein, a facile and cost-effective single-atom iron catalyst (Fe-SA/NC) anchored on nitrogen-doped porous carbon was first fabricated by using waste biomass as a carbon source. The Fe-SA/NC catalyst exhibited outstanding performance with a high turnover frequency of 1.72 min−1 toward antibiotics degradation via peroxymonosulfate activation. ECOSAR program and algae growth experiments demonstrated that the byproducts produced during the sulfamethoxazole degradation process were not detrimental to the aquatic environment. Radical quenching and electron paramagnetic resonance experiments revealed that Fe-SA/NC remarkably promoted 1O2 production in PMS-assisted reaction, and thus 1O2 contributed as much as 78.77% to sulfamethoxazole degradation. As indicated by experiment and density functional theory (DFT) calculations, FeN2O2 configuration serves as the active site. DFT calculations further presented the most rational generation route of 1O2 as PMS→OH* →O* →1O2. We also designed Fe-SA/NC embedded spherical pellets for contaminants elimination at the device level. This study offers new insights into the synthesis of SACs from waste biomass and their practical application in environmental remediation.

Atomically Dispersed Pt-Doped Co3 O4 Spinel Nanoparticles Embedded in Polyhedron Frames for Robust Propane Oxidation at Low Temperature.

This study adopts a facile and effective in situ encapsulation-oxidation strategy for constructing a coupling catalyst composed of atomically dispersed Pt-doped Co3 O4 spinel nanoparticles (NPs) embedded in polyhedron frames (PFs) for robust propane total oxidation. Benefiting from the abundant oxygen vacancies and more highly valent active Co3+ species caused by the doping of Pt atoms as well as the confinement effect, the optimized 0.2Pt-Co3 O4 NPs/PFs catalyst exhibits excellent propane catalytic activity with low T90 (184 °C), superior apparent reaction rate (21.62×108 (mol gcat -1 s-1 )), low apparent activation energy (Ea = 17.89kJ mol-1 ), high turnover frequency( 811×107 (mol gcat -1 s-1 )) as well as good stability. In situ diffuse reflectance infrared Fourier transform spectroscopy and density functional theory calculations indicate that the doping of Pt atoms enhances the oxygen activation ability, and decreases the energy barrier required for CH bond breaking, thus improving the deep oxidation process of the intermediate species. This study opens up new ideas for constructing coupling catalysts from atomic scale with low cost to enhance the activation of oxygen molecules and the deep oxidation of linear short chain alkanes at low temperature.

Electronic metal − support interaction directed electron-deficient nanoparticulate Ru on Ti3C2 MXene-derived TiO2 nanoflowers for robust benzene semi-hydrogenation

Regulating the geometric and electronic configurations of interfacial active sites is an attractive approach to design high-efficiency catalysts. Here, guiding by the electronic metal–support interaction (EMSI), we constructed the chemical state-tunable nanoparticulate Ru on three-dimensional (3D) porous TiO2 nanoflowers derived from 2D Ti3C2 MXene nanosheets (Ru/TMTFs-x). Benefitting by the unique geometric architecture and EMSI-directed electron-deficient configuration of Ru, the catalysts are efficient in benzene semi-hydrogenation, achieving a high turnover frequency (TOF, 7.2 s−1) and an excellent initial cyclohexene selectivity (78%) on the most electron-deficient Ru/TMTFs-773 catalyst. Despite that the TOFs are nearly identical along with the enhancement in electron-deficient degree of Ru on Ru/TMTFs-x by tuning the Ti4+: Ti3+ molar ratios, which was originated from the resemblances in Ru size and acidity, a positive correlation between cyclohexene selectivity and electron-deficient degree of Ru was recognized. By virtue of kinetics analyses and density functional theory (DFT) calculations, the promotion in net generation rate of cyclohexene and the weakening in cyclohexene adsorption on Ru/TMTFs-x when lowering the electron density of Ru are responsible for the selectivity enhancement. A linearity between selectivity and the percentage of Ti4+ sites was identified, further corroborating the EMSI-mediated selectivity enhancement on Ru/TMTFs-x.

Convenient hydrothermal treatment combining with “Ship in Bottle” to construct Yolk-Shell N-Carbon@Ag-void@mSiO2 for high effective Nano-Catalysts

More active sites will be exposed when noble metal particles are loaded on the core of yolk-shell nanospheres (NM-YSNS) to give higher metal utilization rate, catalytic activity, and good recycle stability. Herein, we adopt an efficient strategy to access the high-performance NM-YSNS via “ship in bottle” mindset on loading Ag nanoparticle on the core surface of core–shell structure accurately and the core shrinkage on forming yolk-shell structure. First, we systematically investigated the mechanism of SiO2 coating 3-aminophenol-co-formaldehyde nanoparticles to generate 3-aminophenol-co-formaldehyde@mesoporous SiO2 core–shell nanospheres (3-APF@mSiO2 CSNS). Interestingly, the core surface of 3-APF@mSiO2 CSNS became uneven after hydrothermal process, which provided positions for Ag, then additional Ag+ could reach the 3-APF surface through the mSiO2 shell and be in situ reduced into Ag particles by –NH- and –NH2 there. Similarly, the 3-APF@Au@mSiO2 CSNS were prepared successfully. After carbonizing 3-APF@Ag@mSiO2 CSNS, the N-Carbon@Ag-void@mSiO2 YSNS was obtained. The NM-YSNS catalyst had a high specific surface area of 258.8 m2g−1, mSiO2 shell of 3.8 nm mesoporous size, and core loaded with Ag particles firmly, showing a high turnover frequency of 137.08 h−1 and good recycle stability in catalytic reduction of 4-nitrophenol for preparing 4-aminophenol.

Covalent Triazine Framework Encapsulated Ultrafine PdAu Alloy Nanoclusters as Additive-Free Catalysts for Efficient Hydrogen Production from Formic Acid

Dehydrogenation of formic acid (FA) represents a promising route for clean hydrogen production, the economic viability of which, however, is largely hindered by the catalyst inefficiency. Here, ultrafine Au–Pd bimetallic nanoclusters (NCs) confined within the cavities of bipyridyl covalent triazine frameworks (CTFs) are constructed via a metal-nitrogen coordination reduction strategy, which is enabled by the chelation between bidentate nitrogen sites of the bipyridine ligands and metal ion precursors. The resulting CTF-confined PdAu NCs exhibit a high initial turnover frequency up to 12,368 h–1 (333 K) toward the dehydrogenation of FA without any additives. The experimental and theoretical studies disclose that the pyridinic nitrogen sites of CTF not only facilitate the formation of monodisperse small-sized metal NCs via the anchoring and the pore confinement effect but also serve as a proton buffer which can store excess protons and thus suppress the recombination of adsorbed formate and hydrogen on the PdAu alloy surface. These findings would have significant implications for designing high-performance hydrogen production catalysts.