Ion-regulated electrochemical double layer drives highly selective CO2-to-C2+ conversion.

"… Despite the introduction of high-throughput and combinatorial methods that certainly can be useful in the process of catalysts optimization, it is recognized that the generation of fundamental knowledge at the molecular level is key for the development of new concepts and for reaching the final objective of solid catalysts by design …" Read more in the Editorial by Avelino Corma.

Mesoporous Cu2O microspheres for highly efficient C2 chemicals production from CO2 electroreduction

Electrochemical N2-to-NH3 with high faradaic efficiency on ZrO2/carbon quantum dots catalysts in neutral electrolyte

Highly efficient electrocatalytic CO2-to-ethanol conversion over bimetallic CuPd catalysts via selective CC coupling.

The performance of lithium metal batteries can be significantly enhanced by incorporating fluorinated ether-based electrolytes, yet the solid electrolyte interphase (SEI) formation mechanism on lithium metal surfaces remains elusive. This study employs classical and ab initio molecular dynamics simulations to investigate the decomposition mechanisms of lithium bis(fluoromethanesulfonyl)imide (LiFSI) in 1,2-diethoxyethane (DEE) and its fluorinated analogues, F5DEE and F2DEE, when in contact with lithium metal. Our findings indicate that F5DEE-based electrolytes favor the formation of a FSI-rich primary solvation shell around Li+, while F2DEE-based electrolytes yield a solvent-rich environment. The normalized number density at the Li/electrolyte/Li interface shows a depletion of FSI anions in the electrochemical double layer (EDL) structure near the Li anode upon charging, with the distance between the first main peak of the FSI anion and Li anode following the order F5DEE < DEE < F2DEE. Analysis of the electronic projected density of states and charge transfer dynamics unveils the reductive dissociation pathways of FSI anions and fluorinated DEE solvents on the lithium metal surface, taking into account the influence of the EDL structure. DEE is identified as the most reduction-stable solvent, leading to the selective dissociation of FSI anions and the formation of an entirely inorganic SEI. In contrast, F2DEE displays a pronounced reduction tendency, forming an organic-rich SEI due to the solvent-dominated lowest unoccupied molecular orbital at the interface. F5DEE, competing with FSI anions for reduction, results in the formation of an inorganic-rich hybrid SEI with the highest LiF content. The simulation results correlate well with experimental observations and underscore the pivotal role of various fluorinated functional groups in the formation of EDL and SEI near the lithium metal surface.

Although platinum-based catalysts are highly effective for the oxygen reduction reaction (ORR) in proton exchange membrane fuel cells (PEMFCs), their high cost and scarcity limit large-scale commercialization. As a result, platinum group metal-free catalysts—particularly Fe-N-C materials—have received increasing attention as promising alternatives. Despite significant progress, no platinum-group metal-free (PGM-free) catalyst has yet matched the performance and durability of commercial Pt/C in acidic media. Recent advances in synthesis strategies, however, have led to notable improvements in the activity, stability, and active site density of Fe-N-C catalysts. This review highlights key synthesis approaches, including pyrolysis, MOF-derived templates, and cascade anchoring, and discusses how these methods contribute to improved nitrogen coordination, electronic structure modulation, and active site engineering. The continued refinement of these strategies, alongside improved catalyst screening techniques, is essential for closing the performance gap and enabling the practical deployment of non-PGM catalysts in PEMFC technologies.

Chemoselective hydrogenation of cinnamaldehyde over MOFs-derived M2Si@C (M = Fe, Co, Ni) silicides catalysts

Boosting Electrocatalytic CO ₂ Reduction with Conjugated Bimetallic Co/Zn Polyphthalocyanine Frameworks

Precise control over the distribution of active metal sites on catalyst surfaces is essential for maximizing catalytic efficiency. Addressing the limitations of traditional cluster catalysts with core-embedded catalytic sites, this work presents a strategy to position catalytic sites on the surfaces of oxide clusters. We utilize a calixarene-stabilized titanium-oxo cluster (Ti12L6) as a scaffold to anchor Ag1+ in situ, forming the unique nanocluster Ti12Ag4.5 with six surface-exposed Ag1+ sites. The in situ transformation from Ti12L6 into Ti12Ag4.5 clusters was traced through mass spectrometry, revealing a solvent-mediated dynamic process of disintegration and reassembly of the Ti12L6 macrocycle. The unique Ti12Ag4.5 cluster, featuring a surface-exposed catalytic site configuration, efficiently catalyzes the electroreduction of CO2 to CO over a broad potential window, achieving CO faradaic efficiencies exceeding 82.0% between -0.4 V and -1.8 V. Its catalytic performance surpasses that of bimetallic Ti2Ag2, which features a more conventional design with Ag1+ sites embedded within the cluster. Theoretical calculations indicate that the synergy between the titanium-oxo support and the single Ag1+ sites lowers the activation energy, facilitating the formation of the *COOH intermediate. This work reveals that engineered interactions between active surface metal and the oxide support could amplify catalytic activity, potentially defining a new paradigm in catalyst design.

Enhanced electrochemical CO2 reduction to ethylene over CuO by synergistically tuning oxygen vacancies and metal doping

Electrochemical CO2 conversion to value-added multicarbon (C2+) chemicals holds promise for reducing CO2 emissions and advancing carbon neutrality. However, achieving both high conversion rate and selectivity remains challenging due to the limited active sites on catalysts for carbon-carbon (C─C) coupling. Herein, porous CuO is coated with amorphous CuSiO3 (p-CuSiO3/CuO) to maximize the active interface sites, enabling efficient CO2 reduction to C2+ products. Significantly, the p-CuSiO3/CuO catalyst exhibits impressive C2+ Faradaic efficiency (FE) of 77.8% in an H-cell at -1.2V versus reversible hydrogen electrode in 0.1M KHCO3 and remarkable C2H4 and C2+ FEs of 82% and 91.7% in a flow cell at a current density of 400mA cm-2 in 1M KOH. In situ characterizations and theoretical calculations reveal that the active interfaces facilitate CO2 activation and lower the formation energy of the key intermediate *OCCOH, thus promoting CO2 conversion to C2+. This work provides a rational design for steering the active sites toward C2+ products.

Direct catalytic conversion of glycerol to liquid-fuel classes over Ir–Re supported on W-doped mesostructured silica

Efficient electrocatalytic CO2 reduction to ethanol through the proton coupled electron transfer process of PVnMo(12-n) (n = 1, 2, 3) over indium electrode

Pd-induced polarized Cu0-Cu+ sites for electrocatalytic CO2-to-C2+ conversion in acidic medium

Electroreduction of CO2 in highly acidic environments holds promise for enhancing CO2 utilization efficiency. Due to the HER interference and structural instability, however, challenges in improving the selectivity and stability toward multicarbon (C2+) products remain. In this study, we proposed an "armor protection" strategy involving the deposition of ultrathin, hydrophobic SiO2 onto the Cu surface (Cu/SiO2) through a simple one-step hydrolysis. Our results confirmed the effective inhibition of HER by a hydrophobic SiO2 layer, leading to a high Faradaic efficiency (FE) of up to 76.9% for C2+ products at a current density of 900 mA cm-2 under a strongly acidic condition with a pH of 1. The observed high performance surpassed the reported performance for most previously studied Cu-based catalysts in acidic CO2RR systems. Furthermore, the ultrathin hydrophobic SiO2 shell was demonstrated to effectively prevent the structural reconstruction of Cu and preserve the oxidation state of Cuδ+ active sites during CO2RR. Additionally, it hindered the accumulation of K+ ions on the catalyst surface and diffusion of in situ generated OH- ions away from the electrode, thereby favoring C2+ product generation. In situ Raman analyses coupled with DFT simulations further elucidated that the SiO2 shell proficiently modulated *CO adsorption behavior on the Cu/SiO2 catalyst by reducing *CO adsorption energy, facilitating the C-C coupling. This work offers a compelling strategy for rationally designing and exploiting highly stable and active Cu-based catalysts for CO2RR in highly acidic environments.