Structure-Activity Relationship for Di- up to Tetranuclear Macrocyclic Ruthenium Catalysts in Homogeneous Water Oxidation

Two di- and tetranuclear Ru(bda) (bda: 2,2′-bipyridine-6,6′-dicarboxylate) macrocyclic complexes were synthesized and their catalytic activities in chemical and photochemical water oxidation investigated in a comparative manner to our previously reported trinuclear congener. Our studies have shown that the catalytic activities of this homologous series of multinuclear Ru(bda) macrocycles in homogeneous water oxidation are dependent on their size, exhibiting highest efficiencies for the largest tetranuclear catalyst. The turnover frequencies (TOFs) have increased from di- to tetranuclear macrocycles not only per catalyst molecule but more importantly also per Ru unit with TOF of 6 s⁻¹ to 8.7 s⁻¹ and 10.5 s⁻¹ in chemical and 0.6 s⁻¹ to 3.3 s⁻¹ and 5.8 s⁻¹ in photochemical water oxidation per Ru unit, respectively. Thus, for the first time, a clear structure–activity relationship could be established for this novel class of macrocyclic water oxidation catalysts.     

A Fully Conjugated Covalent Organic Framework with Oxidative and Reductive Sites for Photocatalytic Carbon Dioxide Reduction with Water

Constructing a powerful photocatalytic system that can achieve the carbon dioxide (CO₂) reduction half-reaction and the water (H₂O) oxidation half-reaction simultaneously is a very challenging but meaningful task. Herein, a porous material with a crystalline topological network, named viCOF-bpy-Re, was rationally synthesized by incorporating rhenium complexes as reductive sites and triazine ring structures as oxidative sites via robust −C=C− bond linkages. The charge-separation ability of viCOF-bpy-Re is promoted by low polarized π-bridges between rhenium complexes and triazine ring units, and the efficient charge-separation enables the photogenerated electron–hole pairs, followed by an intramolecular charge-transfer process, to form photogenerated electrons involved in CO₂ reduction and photogenerated holes that participate in H₂O oxidation simultaneously. The viCOF-bpy-Re shows the highest catalytic photocatalytic carbon monoxide (CO) production rate (190.6 μmol g⁻¹ h⁻¹ with about 100 % selectivity) and oxygen (O₂) evolution (90.2 μmol g⁻¹ h⁻¹) among all the porous catalysts in CO₂ reduction with H₂O as sacrificial agents. Therefore, a powerful photocatalytic system was successfully achieved, and this catalytic system exhibited excellent stability in the catalysis process for 50 hours. The structure–function relationship was confirmed by femtosecond transient absorption spectroscopy and density functional theory calculations.     

Water Oxidation by In Situ Generated [RuII(OH2)(NCNHCO)(pic)2]+

A dinuclear ruthenium complex [Ru^II(NC^NHC O)(pic)₂]₂²⁺ ( 2 ) was firstly prepared and characterized spectroscopically and electrochemically. Instead of the conventional ligand exchange, complex 2 dissociates in situ to afford two single‐site Ru aqua complexes, [Ru^II(OH₂)(NC^NHC O)(pic)₂]⁺, which mediates water oxidation through proton‐coupled electron transfer events. In electrokinetic studies, complex 2 demonstrated a TOF of 150.3 s⁻¹ comparable to those state‐of‐the‐art catalysts at neutral conditions. TONs of 2173 and 217 were attained in chemical and photochemical water oxidation when 2 was used as a catalyst, exhibiting good stability. Notably, a TOF of 1.3 s⁻¹ was achieved at CAN‐driven water oxidation, which outperformed most of the reported single‐site Ru complexes, indicating that complex 2 is one of most active water oxidation catalysts (WOCs) to date. The unique coordination configuration and outstanding catalytic performance of complex 2 might shed light on the design of novel molecular WOCs.     

Heterodinuclear Zn(II), Mg(II) or Co(III) with Na(I) Catalysts for Carbon Dioxide and Cyclohexene Oxide Ring Opening Copolymerizations

A series heterodinuclear catalysts, operating without co-catalyst, show good performances for the ring opening copolymerization (ROCOP) of cyclohexene oxide and carbon dioxide. The complexes feature a macrocyclic ligand designed to coordinate metals such as Zn(II), Mg(II) or Co(III), in a Schiff base ‘pocket’, and Na(I) in a modified crown-ether binding ‘pocket’. The 11 new catalysts are used to explore the influences of the metal combinations and ligand backbones over catalytic activity and selectivity. The highest performance catalyst features the Co(III)Na(I) combination, [N,N′-bis(3,3’-triethylene glycol salicylidene)-1,2-ethylenediamino cobalt(III) di(acetate)]sodium ( 7 ), and it shows both excellent activity and selectivity at 1 bar carbon dioxide pressure (TOF=1590 h⁻¹, >99 % polymer selectivity, 1 : 10: 4000, 100 °C), as well as high activity at higher carbon dioxide pressure (TOF=4343 h⁻¹, 20 bar, 1 : 10 : 25000). Its rate law shows a first order dependence on both catalyst and cyclohexene oxide concentrations and a zeroth order for carbon dioxide pressure, over the range 10–40 bar. These new catalysts eliminate any need for ionic or Lewis base co-catalyst and instead exploit the coordination of earth-abundant and inexpensive Na(I) adjacent to a second metal to deliver efficient catalysis. They highlight the potential for well-designed ancillary ligands and inexpensive Group 1 metals to deliver high performance heterodinuclear catalysts for carbon dioxide copolymerizations and, in future, these catalysts may also show promise in other alternating copolymerization and carbon dioxide utilizations.     

Upgrading CO2 by Incorporation into Urethanes through Silver‐Catalyzed One‐Pot Stepwise Amidation Reaction

One‐pot two‐step stepwise reaction of terminal propargylic alcohols, carbon dioxide, and primary/secondary amines for the effective synthesis of various urethanes through robust silver‐catalysed C‐O/C‐N bond formation is reported. Catalytic activities were investigated by controlling catalyst loading, reaction pressure and time, and very high turnover number (turnover frequency) was obtained: 3350 (35 h⁻¹) with 0.01 mol% silver catalyst under 0.1 MPa, and up to 13360 (139 h⁻¹) with 0.005 mol% silver catalyst under 2.0 MPa at room temperature. The strategy was ingeniously regulated, and synchronously afforded a wide range of β‐oxopropylcarbamate and 1,3‐oxazolidin‐2‐one motifs in excellent yields and selectivity together with unprecedented high turnover number (TON) and turnover frequency (TOF) value.     

固载Ru基催化剂上二氧化碳加氢合成甲酸Ⅱ反应条件对催化剂性能的影响

The synthesis of formic acid from carbon dioxide and hydrogen using a silica immobilized ruthenium catalyst as precursor has been studied in different reaction conditions. The results revealed that the TOF （turn over frequency） of HCOOH achieved 1481.5 h^-1 on immobilized ruthenium catalyst near the critical pressure point of CO2 with H2 pressure of 4.0 MPa, reaction temperature of 80℃ and PPh3/Ru molar ratio of 6：1. The reaction activity of immobilized catalyst was higher than that of homogeneous catalyst, and the immobilized catalyst also offered the practical advantages such as easy separation and reuse.     

Electrothermal Water-Gas Shift Reaction at Room Temperature with a Silicomolybdate-Based Palladium Single-Atom Catalyst

The water-gas shift (WGS) reaction is often conducted at elevated temperature and requires energy-intensive separation of hydrogen (H₂) from methane (CH₄), carbon dioxide (CO₂), and residual carbon monoxide (CO). Designing processes to decouple CO oxidation and H₂ production provides an alternative strategy to obtain high-purity H₂ streams. We report an electrothermal WGS process combining thermal oxidation of CO on a silicomolybdic acid (SMA)-supported Pd single-atom catalyst (Pd₁/CsSMA) and electrocatalytic H₂ evolution. The two half-reactions are coupled through phosphomolybdic acid (PMA) as a redox mediator at a moderate anodic potential of 0.6 V (versus Ag/AgCl). Under optimized conditions, our catalyst exhibited a TOF of 1.2 s⁻¹ with turnover numbers above 40 000 mol mol_Pd⁻¹ achieving stable H₂ production with a purity consistently exceeding 99.99 %.     

Two-Dimensional Metal–Organic Framework Nanosheets with Cobalt-Porphyrins for High-Performance CO2 Electroreduction

The electrochemical reduction of CO₂ presents a promising strategy to mitigate the greenhouse effect and reduce excess carbon dioxide emission to realize a carbon-neutral energy cycle, but it suffers from the lack of high-performance electrocatalysts. In this work, catalytic active cobalt porphyrin [TCPP(Co)=(5,10,15,20)-tetrakis(4-carboxyphenyl)porphyrin-Co^II] was precisely anchored onto water-stable 2D metal–organic framework (MOF) nanosheets (Zr-BTB) to obtain ultrathin 2D MOF nanosheets [TCPP(Co)/Zr-BTB] with accessible catalytic sites for the CO₂ reduction reaction. Compared with molecular cobalt porphyrin, the TCPP(Co)/Zr-BTB exhibits an ultrahigh turnover frequency (TOF=4768 h⁻¹ at −0.919 V vs. reversible hydrogen electrode, RHE) owing to high active-site utilization. In addition, three post-modified 2D MOF nanosheets [TCPP(Co)/Zr-BTB-PABA, TCPP(Co)/Zr-BTB-PSBA, TCPP(Co)/Zr-BTB-PSABA] were obtained, with the modifiers of p-(aminomethyl)benzoic acid (PABA), p-sulfobenzoic acid potassium (PSBA), and p-sulfamidobenzoic acid (PSABA), to change the micro-environments around TCPP(Co) through the tuning of steric effects. Among them, the TCPP(Co)/Zr-BTB-PSABA exhibited the best performance with a faradaic efficiency (FE_CO) of 85.1 %, TOF of 5315 h⁻¹, and j_total of 6 mA cm⁻² at −0.769 V (vs. RHE). In addition, the long-term durability of the electrocatalysts is evaluated and the role of pH buffer is revealed.     

Rhodium-terpyridine Catalyzed Transfer Hydrogenation of Aromatic Nitro Compounds in Water

A rhodium terpyridine complex catalyzed transfer hydrogenation of nitroarenes to anilines with i-PrOH as hydrogen source and water as solvent has been developed. The catalytic system can work at a substrate/catalyst (S/C) ratio of 2000, with a turnover frequency (TOF) up to 3360 h⁻¹, which represents one of the most active catalytic transfer hydrogenation systems for nitroarene reduction. The catalytic system is operationally simple and the protocol could be scaled up to 20 gram scale. The water-soluble catalyst bearing a carboxyl group could be recycled 15 times without significant loss of activity.     

Electrocatalytic Reduction of CO2 to Acetic Acid by a Molecular Manganese Corrole Complex

The controlled electrochemical reduction of carbon dioxide to value added chemicals is an important strategy in terms of renewable energy technologies. Therefore, the development of efficient and stable catalysts in an aqueous environment is of great importance. In this context, we focused on synthesizing and studying a molecular Mn^III‐corrole complex, which is modified on the three meso‐positions with polyethylene glycol moieties for direct and selective production of acetic acid from CO₂. Electrochemical reduction of Mn^III leads to an electroactive Mn^II species, which binds CO₂ and stabilizes the reduced intermediates. This catalyst allows to electrochemically reduce CO₂ to acetic acid in a moderate acidic aqueous medium (pH 6) with a selectivity of 63 % and a turn over frequency (TOF) of 8.25 h^?1, when immobilized on a carbon paper (CP) electrode. In terms of high selectivity towards acetate, we propose the formation and reduction of an oxalate type intermediate, stabilized at the Mn^III‐corrole center.     

Synthesis and characterization of dimeric μ-oxidovanadium complexes as the functional model of vanadium bromoperoxidase

Two vanadium (IV) complexes [V^IVO(Haeae-sal)(MeOH)]⁺ ( 1 ) and [V^IVO(Haeae-hyap)(MeOH)]⁺ ( 2 ) were prepared by reacting [VO(acac)₂] with ligands [H₂aeae-sal] ( I ) and [H₂aeae-hyap] ( II ) respectively. Condensation of 2-(2-aminoethylamino)ethanol with salicylaldehyde and 2-hydroxyacetophenone produces the ligands ( I ) and ( II ) respectively. Both vanadium complexes 1 and 2 are sensitive towards aerial oxygen in solution and rapidly convert into vanadium(V) dioxido species. Vanadium(V) dioxido species crystalizes as the dimeric form in the solid-state. Single-crystal XRD analysis suggests octahedral geometry around each vanadium center in the solid-state. To access the benefits of heterogeneous catalysis, vanadium(V) dioxido complexes were anchored into the polymeric chain of chloromethylated polystyrene. All the synthesized neat and supported vanadium complexes have been studied by a number of techniques to confirm their structural and functional properties. Bromoperoxidase activity of the synthesized vanadium(V) dioxido complexes 3 and 4 was examined by carrying out oxidative bromination of salicylaldehyde and oxidation of thioanisole. In the presence of hydrogen peroxide, 3 shows 94.4% conversion ( TOF value of 2.739 × 10² h⁻¹) and 4 exhibits 79.0% conversion (TOF value of 2.403 × 10² h⁻¹) for the oxidative bromination of salicylaldehyde where 5-bromosalicylaldehyde appears as the major product. Catalysts 3 and 4 also efficiently catalyze the oxidation of thioanisole in the presence of hydrogen peroxide where sulfoxide is observed as the major product. Covalent attachment of neat catalysts 3 and 4 into the polymer chain enhances substrate conversion (%) and their catalytic efficiency increases many folds, both in the oxidative bromination and oxidation of thioether. Polymer supported catalysts 5 displayed 98.8% conversion with a TOF value of 1.127 × 10⁴ h⁻¹ whereas catalyst 6 showed 95.7% conversion with a TOF value of 4.675 × 10³ h⁻¹ for the oxidative bromination of salicylaldehyde. These TOF values are the highest among the supported vanadium catalysts available in the literature for the oxidative bromination of salicylaldehyde.     

Plasmon-Induced Radical-Radical Heterocoupling Boosts Photodriven Oxidative Esterification of Benzyl Alcohol over Nitrogen-Doped Carbon-Encapsulated Cobalt Nanoparticles

Selective oxidation of alcohols under mild conditions remains a long-standing challenge in the bulk and fine chemical industry, which usually requires environmentally unfriendly oxidants and bases that are difficult to separate. Here, a plasmonic catalyst of nitrogen-doped carbon-encapsulated metallic Co nanoparticles (Co@NC) with an excellent catalytic activity towards selective oxidation of alcohols is demonstrated. With light as only energy input, the plasmonic Co@NC catalyst effectively operates via combining action of the localized surface-plasmon resonance (LSPR) and the photothermal effects to achieve a factor of 7.8 times improvement compared with the activity of thermocatalysis. A high turnover frequency (TOF) of 15.6 h⁻¹ is obtained under base-free conditions, which surpasses all the reported catalytic performances of thermocatalytic analogues in the literature. Detailed characterization reveals that the d states of metallic Co gain the absorbed light energy, so the excitation of interband d-to-s transitions generates energetic electrons. LSPR-mediated charge injection to the Co@NC surface activates molecular oxygen and alcohol molecules adsorbed on its surface to generate the corresponding radical species (e.g., ⋅O₂⁻, CH₃O⋅ and R-⋅CH-OH). The formation of multi-type radical species creates a direct and forward pathway of oxidative esterification of benzyl alcohol to speed up the production of esters.     

Electrocatalytically Active Fe-(O-C2)4 Single-Atom Sites for Efficient Reduction of Nitrogen to Ammonia

Single-atom catalysts have demonstrated their superiority over other types of catalysts for various reactions. However, the reported nitrogen reduction reaction single-atom electrocatalysts for the nitrogen reduction reaction exclusively utilize metal–nitrogen or metal–carbon coordination configurations as catalytic active sites. Here, we report a Fe single-atom electrocatalyst supported on low-cost, nitrogen-free lignocellulose-derived carbon. The extended X-ray absorption fine structure spectra confirm that Fe atoms are anchored to the support via the Fe-(O-C₂)₄ coordination configuration. Density functional theory calculations identify Fe-(O-C₂)₄ as the active site for the nitrogen reduction reaction. An electrode consisting of the electrocatalyst loaded on carbon cloth can afford a NH₃ yield rate and faradaic efficiency of 32.1 μg h⁻¹ mg_cat.⁻¹ (5350 μg h⁻¹ mg_Fe⁻¹) and 29.3 %, respectively. An exceptional NH₃ yield rate of 307.7 μg h⁻¹ mg_cat.⁻¹ (51 283 μg h⁻¹ mg_Fe⁻¹) with a near record faradaic efficiency of 51.0 % can be achieved with the electrocatalyst immobilized on a glassy carbon electrode.     

Directed Electron Delivery from a Pb-Free Halide Perovskite to a Co(II) Molecular Catalyst Boosts CO2 Photoreduction Coupled with Water Oxidation

The development of high-performance photocatalytic systems for CO₂ reduction is appealing to address energy and environmental issues, while it is challenging to avoid using toxic metals and organic sacrificial reagents. We here immobilize a family of cobalt phthalocyanine catalysts on Pb-free halide perovskite Cs₂AgBiBr₆ nanosheets with delicate control on the anchors of the cobalt catalysts. Among them, the molecular hybrid photocatalyst assembled by carboxyl anchors achieves the optimal performance with an electron consumption rate of 300±13 μmol g⁻¹ h⁻¹ for visible-light-driven CO₂-to-CO conversion coupled with water oxidation to O₂, over 8 times of the unmodified Cs₂AgBiBr₆ (36±8 μmol g⁻¹ h⁻¹), also far surpassing the documented systems (<150 μmol g⁻¹ h⁻¹). Besides the improved intrinsic activity, electrochemical, computational, ex-/in situ X-ray photoelectron and X-ray absorption spectroscopic results indicate that the electrons photogenerated at the Bi atoms of Cs₂AgBiBr₆ can be directionally transferred to the cobalt catalyst via the carboxyl anchors which strongly bind to the Bi atoms, substantially facilitating the interfacial electron transfer kinetics and thereby the photocatalysis.     

Boosting Electrocatalytic Carbon Dioxide Reduction via Self-Relaxation of Asymmetric Coordination in Fe-Based Single Atom Catalyst

Addressing the limitations arising from the consistent catalytic behavior observed for various intermediates during the electrochemical carbon dioxide reduction reaction (CO₂RR) poses a significant challenge in the optimization of catalytic activity. In this study, we aimed to address this challenge by constructing an asymmetric coordination Fe single atom catalyst (SCA) with a dynamically evolved structure. Our catalyst, consisting of a Fe atom coordinated with one S atom and three N atoms (Fe−S₁N₃), exhibited exceptional selectivity (CO Faradaic efficiency of 99.02 %) and demonstrated a high intrinsic activity (TOF of 7804.34 h⁻¹), and remarkable stability. Using operando XAFS spectra and Density Functional Theory (DFT) calculations, we elucidated the self-relaxation of geometric distortion and dynamic evolution of bond lengths within the catalyst. These structure changes enabled independent regulation of the *COOH and *CO intermediate adsorption energies, effectively breaking the linear scale relationship and enhancing the intrinsic activity of CO₂RR. This study provides valuable insights into the dynamic evolution of SACs and paves the way for targeted catalyst designs aimed to disrupt the linear scaling relationships.     

Promoting near-infrared photocatalytic activity of carbon-doped carbon nitride via solid alkali activation

Ultrabroad spectral absorption is required for semiconductor photocatalysts utilized for solar-to-chemical energy conversion. The light response range can be extended by element doping, but the photocatalytic performance is generally not enhanced correspondingly. Here we present a solid alkali activation strategy to synthesize near-infrared (NIR) light-activated carbon-doped polymeric carbon nitride (A-cPCN) by combining the copolymerization of melamine and 1,3,5-trimesic acid. The prepared A-cPCN is highly crystalline with a narrowed bandgap and enhanced efficiency in the separation of photogenerated electrons and holes. Under irradiation with NIR light (780 nm ≥ λ ≥ 700 nm), A-cPCN shows an excellent photocatalytic activity for H₂ generation from water with rate of 165 µmol g⁻¹ h⁻¹, and the photo-redox activity for H₂O₂ production (109 µmol g⁻¹ h⁻¹) from H₂O and O₂, whereas no observed photocatalytic activity over pure PCN. The NIR photocatalytic activity is due to carbon doping, which leads to the formation of an interband level, and the alkali activation that achieved shrinking the transfer distance of photocarriers. The current synergistic strategy may open insights to fabricate other carbon-nitrogen-based photocatalysts for enhanced solar energy capture and conversion.     

Solar-Driven CO2 Conversion via Optimized Photothermal Catalysis in a Lotus Pod Structure

Photothermal CO₂ reduction is one of the most promising routes to efficiently utilize solar energy for fuel production at high rates. However, this reaction is currently limited by underdeveloped catalysts with low photothermal conversion efficiency, insufficient exposure of active sites, low active material loading, and high material cost. Herein, we report a potassium-modified carbon-supported cobalt (K⁺−Co−C) catalyst mimicking the structure of a lotus pod that addresses these challenges. As a result of the designed lotus-pod structure which features an efficient photothermal C substrate with hierarchical pores, an intimate Co/C interface with covalent bonding, and exposed Co catalytic sites with optimized CO binding strength, the K⁺−Co−C catalyst shows a record-high photothermal CO₂ hydrogenation rate of 758 mmol g_cat⁻¹ h⁻¹ (2871 mmol g_Co⁻¹ h⁻¹) with a 99.8 % selectivity for CO, three orders of magnitude higher than typical photochemical CO₂ reduction reactions. We further demonstrate with this catalyst effective CO₂ conversion under natural sunlight one hour before sunset during the winter season, putting forward an important step towards practical solar fuel production.     

Synthesis of Sulfonated Porous Organic Polymers with a Hydrophobic Core for Efficient Acidic Catalysis in Organic Transformations

Synthesis of sulfonated porous polymers with improved hydrophobicity and stability is of extreme importance in both academic research and industrial applications. However, there is often a trade-off between acidity and surface hydrophobicity of sulfonated polymers. In this study, we report a strategy for the synthesis of sulfonated porous organic polymers (S-PT) with improved hydrophobicity via free radical polymerization method by using a rigid and large multidentate monomer, 1,3,5-tri(4-vinylphenyl)-benzene, having a hydrophobic core. The results of vapor adsorption measurement show that S-PT has more hydrophobic properties than sulfonated poly(divinylbenzene) (S-PD), attributed to the hydrophobic core of its multidentate monomer. Furthermore, the optimization of sulfonation time established a balance between surface acidity and hydrophobicity. Under optimized conditions, S-PT afforded up to 113 mmol g⁻¹ h⁻¹ TOF in the esterification of oleic acid with methanol, more active than commercial Amberlyst-15 with TOF of 15 mmol g⁻¹ h⁻¹ and Nafion NR50 with TOF of 7 mmol g⁻¹ h⁻¹. We believe that the findings of this study will provide useful insights to advance the design and synthesis of solid acid catalysts for organic transformations.     

Comprehensive and High-throughput Electrolysis of Water and Urea by 3–5 nm Nickel and Copper Coordination Polymers

Metal-organic coordination polymers (CP) have attracted the scientific attention for electrochemical water oxidation as it has the similar coordination structure like natural photosynthetic coordinated complex. However, the harsh synthesis conditions and bulky nature pose a major challenge in the field of catalysis. Herein, 3–5 nm CP particles synthesized at room temperature using aqueous solutions of Ni²⁺/Cu²⁺ and 2,5-dihydroxyterepthalic acid as precursor were applied for alkaline water and urea electrolysis. The overpotential required is only 300 mV at 10 mA cm⁻² by Nano-Ni CP for water oxidation, with turnover frequency (TOF) of 21.4 s⁻¹ which is around 8 times higher than its bulk-counterpart. Overall water and urea splitting were achieved with Nano-Cu (−) ∥ Nano-Ni (+) couple on Ni foam at 1.69 and 1.52 V to achieve 10 mA cm⁻², respectively. High electrochemical surface area (ECSA), high TOF, and enhanced mass diffusion are found to be the key parameters responsible for the state-of-the-art water and urea splitting performances of nano-CPs as compared to their bulk counterparts.     

Atomically Dispersed Cobalt/Copper Dual-Metal Catalysts for Synergistically Boosting Hydrogen Generation from Formic Acid

The development of practical materials for (de)hydrogenation reactions is a prerequisite for the launch of a sustainable hydrogen economy. Herein, we present the design and construction of an atomically dispersed dual-metal site Co/Cu−N−C catalyst allowing significantly improved dehydrogenation of formic acid, which is available from carbon dioxide and green hydrogen. The active catalyst centers consist of specific CoCuN₆ moieties with double-N-bridged adjacent metal-N₄ clusters decorated on a nitrogen-doped carbon support. At optimal conditions the dehydrogenation performance of the nanostructured material (mass activity 77.7 L ⋅ g_metal⁻¹ ⋅ h⁻¹) is up to 40 times higher compared to commercial 5 % Pd/C. In situ spectroscopic and kinetic isotope effect experiments indicate that Co/Cu−N−C promoted formic acid dehydrogenation follows the so-called formate pathway with the C−H dissociation of HCOO* as the rate-determining step. Theoretical calculations reveal that Cu in the CoCuN₆ moiety synergistically contributes to the adsorption of intermediate HCOO* and raises the d-band center of Co to favor HCOO* activation and thereby lower the reaction energy barrier.