Jul 2026· Small Methods· Vol 10· 0 citations· 54 references
Medicine
Abstract
Electrochemical CO2 reduction offers a route to produce liquid fuels such as methanol; however, strong competition from hydrogen evolution and limited control over key reaction intermediates lead to low single‐product selectivity and poor stability under operating conditions. Heteronuclear dual‐atom catalysts (DACs) have shown great promise in this regard because two neighboring catalyst atoms can cooperatively bind and polarize oxygenated intermediates. Despite these attractive features, DACs often struggle to stabilize the right early intermediate for methanol, so CO2 protonation defaults back to *COOH (and then *CO), which breaks methanol selectivity. Here, we utilize DAC systems stabilized on a carbon nitride (C3N4) framework to resolve this mechanistic bottleneck at the molecular level using density functional theory and constrained molecular dynamics simulations. A Sn–N2/Cu–N2 DAC embedded in a C3N4 framework, coupled to an explicit aqueous interface and evaluated under an applied potential, is shown to favor methanol formation through a six‐electron *OCHO pathway. The neighboring Sn and Cu sites synergistically stabilize a bidentate *OCHO intermediate through Sn─O p‐orbital interactions, while suppressing formation of *COOH. The results provide a clear design rule for methanol‐selective CO2RR: enforce cooperative bidentate binding that locks in *OCHO and redirects the first protonation step away from *COOH and toward methanol.
The electrocatalytic synthesis of amides from abundant small molecules offers a sustainable route for green chemical production, yet faces fundamental challenges due to kinetic competition between C–C and C–N bond formation. Here we show an atomically engineered dual-site catalyst featuring nickel single atoms adjacent to copper nanoclusters (Ni-SA/Cu-NCs) on a nitrogen-doped carbon matrix for efficient CO2 and NO3− co-reduction to acetamide. This architecture enables complementary functions, with Ni sites selectively converting CO2 to CO and neighboring Cu nanoclusters promoting C–C coupling to form the *CCO intermediate while concurrently reducing NO3− to form the *NH2 intermediate. The resulting synergy facilitates rapid intermediate transfer and C–N coupling, delivering an acetamide yield rate of 257.3 mmol h−1 gcat.−1 at an industrial current density of 215.7 mA cm−2, with stable operation over 160 h. In situ spectroscopic studies and theoretical calculations suggest that strong Ni–Cu electronic coupling promotes reactant adsorption and reduces the activation barriers for critical steps, including *CO dimerization and *CCO–*NH2 coupling. This work provides an atomic-level design strategy for multi-site catalysts to steer complex electrocatalytic reactions toward value-added products. Producing amides sustainably from abundant feedstocks remains challenging because carbon–carbon and carbon–nitrogen bond formation competes kinetically. Here, the authors report a dual-site catalyst pairing nickel single atoms with copper nanoclusters that directs CO2 and nitrate co-reduction toward acetamide.
S. Xia, Hao Tan, Jianfang Zhang et al.· Nature Communications· 0 citations
Syngas-to-ethanol conversion is economically attractive yet remains challenging due to limited activity and selectivity under practical conditions. Achieving selective C-C coupling and directing *CHO hydrogenation to ethanol require precise control of active-site geometry and electronics. Here we use a coordination–precursor–mediated strategy to construct Ru dual-atom catalysts on N-coordinated carbon supports with tunable local architectures, where the Ru-Ru separation serves as a primary descriptor—together with coordination environment and intersite electronic coupling—governing cooperative CO/H2 activation and C-C bond formation. Varying the interatomic distance modulates geometric confinement and electronic interactions, improving ethanol formation. Within the optimal reaction window, the catalyst with the shortest Ru-Ru distance exhibits high CO conversion, high ethanol selectivity among oxygenated products, with oxygen-free hydrocarbon products excluded from the selectivity normalization, and stable operation at 1.0 MPa. In situ spectroscopy and DFT reveal that short Ru-Ru spacing enhances d-orbital hybridization and confinement, facilitating synergistic back-donation that lowers the C-C coupling barrier; Bader/charge-density analyses indicate preferential stabilization of hydroxylated intermediates toward ethanol. This work highlights distance-tuned dual-atom cooperativity as a key lever for selective syngas-to-ethanol catalysis. Syngas-to-ethanol conversion is economically attractive yet remains challenging due to limited activity and selectivity under practical conditions. Here the authors construct Ru dual-atom catalysts on N-coordinated carbon supports with tunable local architectures for cooperative CO/H2 activation and C–C bond formation.
Haobo Zhao, Yi Wang, Yanling Gao et al.· Nature Communications· 0 citations
ABSTRACT Electrochemical CO2 reduction offers a sustainable route to convert greenhouse gas into high‐value‐added chemicals, yet product distributions remain largely limited to simple C1‐C3 molecules. Here, we report a new reaction in which CO2 reduction intermediates undergo direct C‐C coupling with an external carbon nucleophile under electrochemical conditions. Using cobalt phthalocyanine supported on multi‐walled carbon nanotubes (CoPc/MWCNT) as a catalyst, cyanide ions intercept deeply reduced C1 intermediates to produce glycolonitrile at 4°C with a faradaic efficiency (FE) of up to 6.6%. Combined electrochemical analysis, control experiments, and density functional theory calculations identify *CH2O as the key coupling intermediate, revealing a C‐C coupling mechanism fundamentally different from conventional coupling pathways in CO2 electroreduction to synthesize C2+ compounds. Extending this concept to a three‐component reaction involving hydroxylamine (NH2OH) enables electrocatalytic synthesis of glycine under ambient pressure with a FE of 2.8%. This work establishes a new strategy for constructing complex carbon skeletons directly from CO2 and external nucleophiles, expanding the synthetic scope of electrochemical carbon conversion.
Gongbo Liu, Liuru Fang, Dayu Zhu et al.· Advancement of science· 0 citations
The electrochemical reduction of CO2 has received significant scientific interest over the past two decades as a key step in the synthesis of CO2 into combustible fuels. Cobalt phthalocyanine (CoPc) adsorbed on carbon nanotubes has risen as a rare electrocatalyst that reduces CO2 beyond two electrons, specifically to methanol. Recent efforts have improved the efficiency of this process and established that methanol production proceeds by reduction of a free CO intermediate, however, many aspects of the catalytic pathway remain unclear, which may underpin persistent issues of stability and selectivity. Here we employ electrochemistry, spectroelectrochemistry, X-ray adsorption spectroscopy (XAS), synthesis of catalytic intermediates, and density functional theory (DFT) calculations to understand the catalytic mechanism and identify distinguishing molecular features. We find that CoPc undergoes three sequential reductions between 0 and -2.5 vs NHE; the first reduction occurring at the Co center, and the second two reductions populating the Pc ring. XAS and theory show the Pc ligand to be noninnocent, interacting with the electronic structure of the Co center and causing Co to adopt a Co(II) state as the complex undergoes the second and third reductions. Consistent with previous studies, [CoPc]2- is found to be active for CO2 reduction, however, we find that the catalyst must be reduced further to [CoPc]3- to bind CO at the Co site. Carbonylation of [CoPc]3- under aprotic conditions leads to fast decomposition, forming [Co(CO)4]-. However, we show that [CoPc]3-, if ring protonated by weak acid to form [CoPc-H]2-, reacts with CO to generate a formyl without decomposition, the first step in methanol synthesis. DFT calculations of the mechanism indicate that the reaction of [CoPc-H]2- with CO to generate the formyl in solution proceeds by an intermolecular proton transfer between the Pc ring of [CoPc-H]2- and the Co-CO of [Co-COPc-H]2-. Overall, this study points to the importance of the Pc ligand in determining the catalytic behavior of CoPc and provides the first examples of several isolated reduced CoPc complexes and catalytic intermediates that we hope will guide future work.
Emile E. DeLuca, Cheolwoo Park, Pooja Basera et al.· Journal of the American Chem...· 0 citations
The electrochemical reduction reaction of CO (eCORR) to acetate is a pivotal pathway for carbon neutrality, yet it is persistently constrained by the linear scaling relations of the adsorption energetics of key intermediates. Consequently, conventional alloy catalysts often suffer from an activity-selectivity trade-off, failing to stabilize C─C coupling intermediates without poisoning active sites. Herein, we circumvent this thermodynamic limit by constructing atomically asymmetric Pd1─O─Cu interfaces derived from the partial operando reconstruction of a metal-organic framework (CuPd-THQ), where isolated Pd single atoms are anchored on Cu2O nanoislands (Pd/Cu2O/CuPd-THQ). The strong CO affinity of Pd drives the migration of remote *CO species toward the Pd center via a spillover effect. This catalyst achieves an industrial-level acetate Faradaic efficiency of 82.3% (purity of 96%) and sustains performance for over 400 h at 250 mA cm-2 under -1.0 V versus RHE, significantly outperforming conventional Cu-based catalysts. Furthermore, in a membrane electrode assembly (MEA) system, it delivers a remarkable acetate yield rate of 6367.7 mg L-1 h-1, demonstrating scalable viability. Mechanism studies reveal that this atomic-scale geometric isolation allows for the independent optimization of *CO and *CCO binding energetics. Our findings provide a generalizable strategy for breaking scaling relations in complex multi-electron electrocatalysis.
Electrochemical CO2 reduction (eCO2R) powered by renewable electricity offers a sustainable route for carbon cycling and value-added chemical synthesis. Among possible products, methane (CH4) is particularly attractive due to its high energy density and direct compatibility with existing natural gas infrastructure. However, it remains challenging to selectively produce CH4 with conventional copper catalysts. Herein, we developed a copper-phenolic network catalyst featuring atomically dispersed Cu─O4 sites, where adjacent uncoordinated hydroxyl groups from tannic acid (TA) act as intrinsic hydrogen-bond donors to stabilize the oxygen-bound formate intermediate (*OCHO). This hydrogen-bond-enabled microenvironment redirects eCO2R from the conventional *CO-mediated pathway toward a formate-derived route, while simultaneously suppressing the competing hydrogen evolution reaction. As a result, the optimized Cu-PTA catalyst delivers a high CH4 Faradaic efficiency of 75.5% with a partial current density of 302.0 mA cm-2 in aqueous electrolyte. Notably, this pathway-steering strategy is readily applicable to deuterated electrolytes, enabling efficient production of deuterated methane (CD4) with a record-high Faradaic efficiency of 83.1% and a partial current density of 415.6 mA cm-2. This work establishes hydrogen-bond engineering as a general approach for manipulating reaction pathways through local stabilization of oxygen-bound intermediates toward sustainable synthesis of high-value chemicals.
