Conventional catalyst design for CO2 electroreduction is fundamentally constrained by the pH of the bulk electrolyte as it affects catalyst durability, reaction pathways, and overall performance. Herein, we break this paradigm by using three-dimensional ordered porous Cu2O octahedra (3DOP Cu2O-OC) to decouple the local reaction microenvironment from the bulk electrolyte. This architecture synergistically integrates a built-in electric field and nanoconfinement effects, which work in concert to enrich electrolyte cations and enhance local CO2 concentration, thereby creating a stable microenvironment independent of the electrolyte pH. Moreover, the C-C coupling reaction via forming a *OCCOH intermediate is kinetically promoted at the defective Cu+/Cu0 interface sites confined in the nanopores. Leveraging these synergistic effects, 3DOP Cu2O-OC achieves high Faradaic efficiencies of 84.0 ± 1.0% in alkaline and 74.0 ± 0.2% in acidic electrolytes for multicarbon products at current densities up to -1.0 and -0.8 A cm-2, respectively. This work establishes a general design model for creating adaptive microenvironments by leveraging synergistic physical effects within nanoarchitectures, providing an important design principle for universal electrocatalyst design.

The success of electrochemical CO2 reduction at high current densities hinges on precise interfacial transportation and the local concentration of gaseous CO2. However, the creation of efficient CO2 transportation channels remains an unexplored frontier. In this study, we design and synthesize hydrophobic porous Cu2O spheres with varying pore sizes to unveil the nanoporous channel's impact on gas transfer and triple-phase interfaces. The hydrophobic channels not only facilitate rapid CO2 transportation but also trap compressed CO2 bubbles to form abundant and stable triple-phase interfaces, which are crucial for high-current-density electrocatalysis. In CO2 electrolysis, in situ spectroscopy and density functional theory results reveal that atomic edges of concave surfaces promote C-C coupling via an energetically favorable OC-COH pathway, leading to overwhelming CO2-to-C2+ conversion. Leveraging optimal gas transportation and active site exposure, the hydrophobic porous Cu2O with a 240 nm pore size (P-Cu2O-240) stands out among all the samples and exhibits the best CO2-to-C2+ productivity with remarkable Faradaic efficiency and formation rate up to 75.3 ± 3.1% and 2518.2 ± 8.1 μmol h-1 cm-2, respectively. This study introduces a novel paradigm for efficient electrocatalysts that concurrently addresses active site design and gas-transfer challenges.

Metal-free catalysts offer a desirable alternative to traditional metal-based catalysts. However, it remains challenging to improve the catalytic performance of metal-free catalysts to be as promising as that of metal-based materials. Herein, a polymer-assisted method followed by pyrolysis treatment was employed to synthesize nitrogen (N)-doped porous carbon nanoflowers with nanosheet subunits. Leveraging the unique geometry structure and abundant pyridinic-N active sites, the optimized catalyst exhibits a good half-wave potential of 0.85 V versus reversible hydrogen electrode (vs. RHE) and long-term stability with only 17.0 mV negative shift of the half-wave potential after 10 000 cyclic voltammetry cycles in alkaline electrolyte. This research presents a viable strategy for advancing metal-free catalysts.

Targeted for superior formate production from electrochemical carbon dioxide (CO 2 ) reduction, hollow ordered porous copper sulfide cuboctahedra (HOP CuS-CO) with controlled shell thicknesses were designed and synthesized in this study. Uniform and interconnected pores are evenly distributed in the hollow shells of HOP CuS-CO. Capitalizing on the merits of porous cages, HOP CuS-CO exhibit outstanding formate production with a Faradaic efficiency up to 70.3 % and catalytic stability of 26 h under an applied potential of -1.1 V versus reversible hydrogen electrode (vs. RHE). In situ Raman spectroscopy results reveal that the adsorption of HCOO* intermediates is promoted on the catalyst surfaces of HOP CuS-CO due to a spatial confinement effect, which leads to highly efficient CO 2 to formate conversion. The present study offers insights for designing materials toward superior formate production from electrochemical CO 2 reduction.

ADVERTISEMENT RETURN TO ARTICLES ASAPPREVFirst ReactionsNEXTSurface Curvature Matters in Electrochemical ReactionsElectrooxidation of ethynylbenzenes to α,α-dichloketone in seawater was realized by the local electric field evoked from high-curvature NiCo2O4 nanocones.Cuiling Li​Cuiling LiCAS Key Laboratory of Bio-Inspired Materials and Interface Science, Technical Institute of Physics and Chemistry, Chinese Academy of Sciences, Beijing 100190, ChinaEmail: [email protected]More by Cuiling Lihttps://orcid.org/0000-0003-2283-579X and Yusuke Yamauchi​Yusuke YamauchiAustralian Institute for Bioengineering and Nanotechnology (AIBN), The University of Queensland, Brisbane 4072, AustraliaDepartment of Materials Process Engineering, Graduate School of Engineering, Nagoya University, Furo-cho, Chikusa-ku, Nagoya, Aichi 464-8603, JapanEmail: [email protected]More by Yusuke Yamauchihttps://orcid.org/0000-0001-7854-927XCite this: ACS Cent. Sci. 2024, XXXX, XXX, XXX-XXXPublication Date (Web):January 10, 2024Publication History Published online10 January 2024https://doi.org/10.1021/acscentsci.3c01637Published 2024 by American Chemical Society. This publication is licensed under CC-BY 4.0. License Summary*You are free to share (copy and redistribute) this article in any medium or format and to adapt (remix, transform, and build upon) the material for any purpose, even commercially within the parameters below:Creative Commons (CC): This is a Creative Commons license.Attribution (BY): Credit must be given to the creator.View full license*DisclaimerThis summary highlights only some of the key features and terms of the actual license. It is not a license and has no legal value. Carefully review the actual license before using these materials. This publication is Open Access under the license indicated. Learn MoreArticle Views-Altmetric-Citations-LEARN ABOUT THESE METRICSArticle Views are the COUNTER-compliant sum of full text article downloads since November 2008 (both PDF and HTML) across all institutions and individuals. These metrics are regularly updated to reflect usage leading up to the last few days.Citations are the number of other articles citing this article, calculated by Crossref and updated daily. Find more information about Crossref citation counts.The Altmetric Attention Score is a quantitative measure of the attention that a research article has received online. Clicking on the donut icon will load a page at altmetric.com with additional details about the score and the social media presence for the given article. Find more information on the Altmetric Attention Score and how the score is calculated. Share Add toView InAdd Full Text with ReferenceAdd Description ExportRISCitationCitation and abstractCitation and referencesMore Options Share onFacebookTwitterWechatLinked InReddit PDF (1 MB) Get e-AlertscloseSUBJECTS:Catalysts,Chlorine,Electric fields,Electrochemical synthesis,Electrodes Get e-Alerts

Electrochemically converting CO 2 to value-added multi-carbon (C 2+ ) fuels and chemicals is a favorable way to achieve carbon neutrality. Herein, polyaniline/CuO nanosheets (PANI/CuO NSs) hybrid electrocatalysts are developed in order to achieve superior C 2+ selectivity by imparting PANI functional component to the CuO NSs. The decorated PANI nanoparticles (NPs) can effectively stabilize the *CO intermediates and increase their coverage on the active Cu sites, which facilitates the C–C coupling to form multi-carbon products. Benefiting from the synergetic effect of PANI and CuO NSs, best Faradaic efficiency (FE) for C 2+ product up to 66.4% at −1.6 V vs. reversible hydrogen electrode (RHE) in a H-cell measurement and 60.0% at 400 mA·cm −2 in a flow cell measurement are demonstrated by PANI/CuO NSs-25 sample. More importantly, the C 2+ selectivity keeps stable even in a continuous measurement time period of 92 h in H-cell measurement. The present study may provide more insights for designing efficient hybrid materials toward superior C 2+ production from electrocatalytic CO 2 reduction.

The accessibility of active sites is crucial to electrochemical applications, therefore, rationally controlled synthesis of novel electrocatalysts with favorable mass transfer and active site exposure is imperative. In this work, ordered macroporous N-doped carbonous skeletons implanted with dual-phase Co/CoFe nanoparticles are successfully synthesized by directly pyrolyzing Fe3+-incorporated ZIF-67 (ZIF = zeolitic imidazolate framework), which are pre-synthesized by confined growth of Fe3+/ZIF-67 inside the ordered voids of well-assembled polystyrene template. The incorporated Fe species not only benefits the formation of dual-phase Co/CoFe active sites, but also activates the carbon skeletons by enhancing the content of pyridine-N. Benefiting from the favorable accessibility of these active sites caused by the macroporous structure, the Co/CoFe2.5@OMNC sample exhibits good performance toward oxygen reduction reaction (ORR) with four-electron transfer pathway. More importantly, the Co/CoFe2.5@OMNC sample retains the activity even after 10,000 sweeping cycles of durability test, which outperforms commercial Pt/C-20% and other samples.

Imposing phase engineering to porous materials is promising to realize outperforming electrocatalytic performances by taking advantages of the merits of porous nanoarchitecture and heterophase structure. In this work, amorphous/crystalline ruthenium oxide (RuO2) porous particles with rationally regulated heterophases are successfully prepared by integrating the phase engineering into the porous material synthesis. The resultant defect-rich amorphous/crystalline RuO2 porous particles exhibit excellent electrocatalytic performance toward the oxygen evolution reaction, achieving a low overpotential of 165 mV at a current density of 10 mA·cm−2 and a high mass activity up to 133.8 mA·cm−2 at a low overpotential of 200 mV. This work indicates that the synergistic effect of amorphous/crystalline heterophase and porous structural characteristics enables RuO2 to trigger a superior electrocatalytic activity.

Selective conversion of carbon dioxide (CO2) to multi-carbon products (CO2-to-C2+) at high current densities is in essential demand for the practical application of the resultant valuable products, yet it remains challenging to conduct due to the lack of efficient electrocatalysts. Herein, three-dimensional ordered porous cuprous oxide cuboctahedra (3DOP Cu2O-CO) were designed and synthesized by a molecular fence-assisted hard templating approach. Capitalizing on the merits of interconnected and uniformly distributed pore channels, 3DOP Cu2O-CO exhibited outstanding electrochemical CO2-to-C2+ conversion, achieving faradaic efficiency and partial current density for C(2+ )products of up to 81.7% and -0.89 A cm(-2), respectively, with an optimal formation rate of 2.92 mmol h(-1) cm(-2) under an applied current density of -1.2 A cm-2. In situ spectroscopy and simulation results demonstrated that the ordered pores of 3DOP Cu2O-CO can effectively confine and accumulate sufficient *CO adsorption during electrochemical CO2 reduction, which facilitates efficient dimerization for the formation of C2+ products. Furthermore, the 3DOP structure induces a higher local pH value, which not only enhances the C-C coupling reaction, but also suppresses competing H-2 evolution.

Post-neurosurgical infection is a common complication of neurosurgery, and serious infection can threaten the life of patients. In recent years, the increase in multidrug-resistant bacteria, especially carbapenem-resistant Enterobacteriaceae (CRE), has proved fatal to patients. Although there are a few cases of CRE meningitis and few clinical trials have been carried out, it has attracted increasing attention with the increasing probability of its occurrence, especially considering that there are few successful cases. An increasing number of studies are also looking for the risk factors and clinical symptoms of CRE intracranial infection. In terms of treatment, some new antibiotics are gradually being used in the clinic, but due to the complicated drug-resistant mechanism of CRE and the obstruction of the blood‒brain barrier (BBB), the therapeutic effect is still very poor. In addition, obstructive hydrocephalus and brain abscess caused by CRE meningitis are still important causes of patient death and are also difficult to treat.

An effective yet simple approach was developed to synthesize mesoporous PdBi nanocages for electrochemical applications. This technique relies on the subtle utilization of the hydrolysis of a metal salt to generate precipitate cores in situ as templates for navigating the growth of mesoporous shells with the assistance of polymeric micelles. The mesoporous PdBi nanocages are then obtained by excavating vulnerable cores and regulating the crystals of mesoporous metallic skeletons. The resultant mesoporous PdBi nanocages exhibited excellent electrocatalytic performance toward the ethanol oxidation reaction with a mass activity of 3.56 A mg(-1)_Pd, specific activity of 17.82 mA cm(-2) and faradaic efficiency of up to 55.69% for C1 products.

Nanoporous nanoparticles with their surfaces open to reagents enable good electron/mass transport and overall resistance to aggregation, thus they are significantly important in electrocatalytic applications.

Developing electrocatalysts that can completely oxidize ethanol oxidation is critical for commercializing direct ethanol fuel cells. Here, we tailored synthesis of mesoporous PdBi films by employing an electrochemical-assisted micelle assembly approach. The as-prepared film exhibited superior electrocatalytic activity and stability toward ethanol oxidation reaction, which is promising forpractical applications.

The crystal phase of noble metals has been identified as one of the key parameters that can greatly affect their properties and functionalities. However, research on the crystal-phase-dependent catalytic activities of noble metals has been rarely reported. Here, we report a systematic study of surface-plasmon-driven hot-electron-induced photocatalytic reduction of para-nitrothiophenol (pNTP) to p,p'-dimercaptoazobenzene under visible light on Au nanostructures with different crystal phases by in-situ surface-enhanced Raman spectroscopy (SERS). Our results indicate that the photocatalytic rate of unconventional 4H Au is nearly 6-8 times that of conventional face-centered cubic (fcc) Au, suggesting the greater activity of hot electrons on 4H Au. Further electrochemical reductions of pNTP on the 4H and fcc Au nanostructures in aqueous solutions also confirm the higher catalytic activity of the 4H Au. Our study demonstrates that the synthesis of Au nanomaterials with controlled crystal phases paves the way for developing highly efficient catalyst.

With the ever-increasing growth in next-generation flexible and wearable electronics, fiber-shaped zinc-air batteries have attracted considerable attention due to their advantages of high energy density and low cost, though their development, however, has been seriously hampered by the unavailability of efficient electrocatalysts. In this work, we designed a trimetallic nitride electrocatalyst in an unusual molecular sheet form, which was stabilized by metallic titanium carbide sheets. Besides the expected elevation in catalytic activity toward the oxygen evolution reaction, the material simultaneously unlocked excellent catalytic activity for oxygen reduction reaction with the half-wave potential as small as 0.84 V. A flexible fiber-shaped zinc-air battery, employing the designed electrocatalyst as the air cathode and a gel as the electrolyte, demonstrated an enhanced and durable electrochemical performance, outputting a competitive energy density of 627 Wh kgzn-1. This work opens new avenues for utilizing two-dimensional sheets in future wearable and portable device applications.

School of Chemistry and Chemical Engin Beijing 100081, China Key Laboratory of Eco-chemical Engineeri Engineering, Qingdao University of Scie 266042, China International Center for Materials Nan Institute for Materials Science (NIMS), 1-1 N School of Chemical Engineering and Aus Nanotechnology (AIBN), University of Quee E-mail: y.yamauchi@uq.edu.au Australian Nuclear Science and Technology Lucas Heights, NSW 2234, Australia Department of Plant & Environmental New Deogyeong-daero, Giheung-gu, Yongin-si, Gy † Electronic supplementary informa 10.1039/c8sc03911a Cite this: Chem. Sci., 2019, 10, 4054

Recently, crystal-phase engineering has been emerging as a promising strategy to tune the physicochemical properties of noble metal catalysts and further improve their catalytic performance. However, the synthesis of noble metal catalysts with an unconventional crystal phase as well as desired composition and morphology still remains a great challenge. Herein, a series of PdM (M = Zn, Cd, ZnCd) nanosheets (NSs) with thickness less than 5 nm have been synthesized via a facile one-pot wet-chemical method. In particular, different from the conventional face -centered cubic (fcc) phase, PdM NSs possess an unconventional face-centered tetragonal (fct) phase. As a proof-of-concept application, the fct PdZn NSs exhibit significantly enhanced mass activity and stability in ethanol oxidation reaction, compared to the pure Pd NSs and commercial Pd black catalyst.

Mesoporous metals have attracted a lot of interest due to their wide range of applications, particularly in catalysis. We previously reported the preparation of mesoporous Pd using block copolymer micelle templates (Chem. Sci. 2019, 10, 4054). Here we extend this synthetic concept to generate alloyed spherical palladium copper (PdCu) nanoparticles with an open porous network and uniform morphology. This one-pot synthesis is initiated by water-induced micellization of the block copolymer, followed by the chemical reduction, nucleation, and growth of mesoporous spherical alloy nanoparticles. Porosity enables accessibility to numerous active sites throughout the interior and exterior surfaces of the nanoparticles. Mesoporous nanoparticles composed of Pd and Cu alloy exhibit enhanced electrocatalytic activity and stability in the ethanol oxidation reaction (EOR) and the oxygen reduction reaction (ORR).

Dendritic platinum (Pt) nanoparticles are successfully anchored on Ketjen Black by a facile synthetic route without organic solvent. The nonionic surfactant Brij 58 is used as a mesopore-forming agent during the in-situ growth of Pt nanoparticles. The dendritic Pt nanoparticles on Ketjen Black exhibit highly efficient electrocatalytic activity for the oxygen reduction reaction. The electrocatalytic activity can be further improved by increasing the Pt loading amount on Ketjen Black. Upon increasing to 31.4 wt% Pt, the half-wave potential and limited-diffusion current density reach 0.887 V and 6.22 mA cm(-2), respectively. The as-prepared catalyst shows an ideal four-electron pathway of O-2 reduction to H2O and a low H2O2 yield of less than 1% in the potential window of 0.2-0.8 V. Moreover, the catalyst exhibits remarkable long-term durability with the same limiting current density and only a 10.5 mV negative shift in the half-wave potential after 5000 cycles.