Hierarchical Porous Structure Research Articles

Encapsulated Pd clusters in S-1 promote the reactivity of chemical looping via synergistic effect of catalysis and oxygen storage

Chemical looping reforming of CH4 coupled with CO2 reduction technology offers a compelling way for effective CO2 emission with the production of syngas and CO. However, the reaction temperature in chemical looping is relatively higher (>800 °C). To solve this problem, it is critical to explore efficient oxygen carriers. In this work, 3DOM LF0.85N0.15/Pd@S-1 oxygen carrier with hierarchical pore structure obtained high reactivity. 3DOM LF0.85N0.15/Pd@S-1 contained three major components, playing different roles. The 3DOM LF0.85N0.15 with ordered macroporous structure possessed excellent oxygen storage capacity and diffusion property. Pd clusters as active sites promoted CH4 activation and strengthen Lewis acid sites. Silicalite-1 zeolite, with larger surface area and well-defined microporous structure, exhibited superior adsorption properties and used as an ideal support to encapsulate Pd clusters. The well-dispersed Pd clusters further strengthened the reducibility at low temperature. Among all samples, 3DOM LF0.85N0.15/Pd@S-1 exhibited highest reactivity and stability during the successive chemical looping.

Potassium Ion-Assisted Self-Assembled MXene-K-CNT Composite as High-Quality Sulfur-Loaded Hosts for Lithium-Sulfur Batteries.

We successfully synthesized hybrid MXene-K-CNT composites composed of alkalized two-dimensional (2D) metal carbide and carbon nanotubes (CNTs), which were employed as host materials for lithium-sulfur (Li-S) battery cathodes. The unique three-dimensional (3D) intercalated structure through electrostatic interactions by K+ ions in conjunction with the scaffolding effect provided by CNTs effectively inhibited the self-stacking of MXene nanosheets, resulting in an enhanced specific surface area (SSA) and ion transport capability. Moreover, the addition of CNTs and in situ-grown TiO2 considerably improved the conductivity of the cathode material. K+ ion etching created a more hierarchical porous structure in MXene, which further enhanced the SSA. The 3D framework effectively confined S embedded between nanosheet layers and suppressed volume changes of the cathode composite during charging/discharging processes. This combination of CNTs and alkalized nanosheets functioned as a physical and chemical dual adsorption system for lithium polysulfides (LiPSs). When subjected to a high current at 1.0C, S@MXene-K-0.5CNT with S-loaded of 1.2 mg cm-2 had an initial capacity of 919.6 mAh g-1 and capacity decay rate of merely 0.052% per cycle after 1000 cycles. Moreover, S@MXene-K-0.5CNT maintained good cycling stability even at a high current of up to 5.0C. These impressive results highlight the potential of alkalized 2D MXene nanosheets intercalated with CNTs as highly promising cathode materials for Li-S batteries. The study findings also have prospects for the development of next-generation Li-S batteries with high energy density and prolonged lifespans.

Hollow and Porous N‐Doped Carbon Framework as Lithium‐Sulfur Battery Interlayer for Accelerating Polysulfide Redox Kinetics

AbstractLithium‐sulfur batteries (LSBs) have become one of the most powerful candidates for next‐generation battery technologies due to their high theoretical energy density and low cost. However, the notorious shuttle effect of soluble lithium polysulfides (LiPSs) and sluggish conversion reaction kinetics cause low sulfur utilization and inferior cycle life. Rational catalyst design on hierarchical pore structures and composition optimization is highly desired to realize synergetic enrichment, accommodation, and catalytic redox capacity of sulfur species. In this consideration, the hollow and porous N‐doped carbon framework is prepared, in which Co nanoparticles (NPs) are evenly embedded (denoted as Co‐HMCF) to modulate electron cloud density of carbons. Electrochemical tests and density functional theory (DFT) calculations demonstrate that Co‐HMCF could simultaneously deliver superior catalytic activity in accelerating LiPSs conversion as well as Li2S nucleation/decomposition to improve overall sulfur redox kinetics. Consequently, the Co‐HMCF interlayer significantly improves the battery performance, including high discharge capacity output (1538 mAh g−1 at 0.2 C), stable long‐term cycle (0.047% capacity decay per cycle for 800 cycles at 1.0 C), and exceptional rate capacity (582 mAh g−1 at 5.0 C).

Solvothermal synthesis of CuS nanosheets loaded porous carbon electrode composites for high performance supercapacitors

In this work, an electrode composite (CuS-NPC) for supercapacitors was synthesized by loading hexagonal nano-sheeted copper sulfide onto porous carbon through a solvothermal reaction using thiourea and copper acetate as the sulfur and copper sources, respectively. The synergistic effect of nanoscale copper sulfide sheet and hierarchical pore structure of porous carbon with high surface area achieves excellent capacitive performance in electrochemical reactions. CuS-NPC exhibited a large specific capacitance of 1298.7F g−1 at current density of 0.5 A/g and 766.3F g−1 at current density of 10 A/g, revealing that the electrode composite of copper sulfide and porous carbon have a great prospect as a supercapacitor electrode material.

Polymer-incorporated modified halloysite nanotubes for efficient CO2/N2 separation

Mixed-matrix membranes (MMMs) as one of solid sorbents for carbon dioxide (CO2) separation face the challenge of merging efficient separation with economical preparation process using scalable raw material. Halloysite nanotubes (Hal) with unique one-dimensional gas transmission channels have great prospect in MMMs for gas separation. However, the insufficient porosity of Hal has restricted further development of CO2 separation performances. Herein, a facile and efficient modification approach was carried out, involving successive treatments of calcination and selective leaching. The resulting nanotubes with continuous channel systems (CA-Hal) are embedded in poly(ether-block-amide) for the preparation of mixed-matrix membranes with enhanced gas transport. The performances of MMMs with modified nanotubes as inorganic fillers obtained by different modification methods (calcination, selective leaching, and a combination of calcination and selective leaching) were specifically discussed. CA-Hal with the highest specific surface area and certain surface energy has an excellent potential as inorganic fillers, which can be uniformly dispersed in the polymer matrix to form interfacial channels, preventing the particle agglomeration and producing non-selective interfacial defects. The hierarchical porous structure of CA-Hal can serve as fast gas transport channels in MMMs for efficient CO2 diffusion and enhanced separation. The MMMs containing 5 wt% CA-Hal have demonstrated excellent CO2 permeability (179.5 Barrer), CO2 diffusivity (17.56 10−7 cm2·S−1) and CO2/N2 selectivity (98.7). In addition, the prepared MMMs exhibits improved mechanical properties compared with the pure membrane without inorganic fillers.

Stable Hierarchical Porous Heterostructure Ni2P/NC@CoNi2S4 Fabricated via the NiCo-LDH Template Strategy for High-Performance Supercapacitors.

Transition metal phosphide/sulfide (TMP/TMS) heterostructures are attractive supercapacitor electrode materials due to their rapid redox reaction kinetics. However, the limited active sites and weak interfacial interactions result in undesirable electrochemical performance. Herein, based on constructing the NiCo-LDH template on Ni-MOF-derived Ni2P/NC, Ni2P/NC@CoNi2S4 with a porous heterostructure is fabricated by sulfurizing the intermediate and is used for supercapacitors. The exposed Ni sites in the phosphating-obtained Ni2P/NC coordinate with OH- to in situ form an intimate-connected Ni2P/NC@NiCo-LDH, and the CoNi2S4 nanosheets retaining the original cross-linked structure of NiCo-LDH integrate the porous carbon skeleton of Ni2P/NC to yield a hierarchical pore structure with rich electroactive sites. The conducting carbon backbone and the intense electronic interactions at the interface accelerate electron transfer, and the hierarchical pores offer sufficient ion diffusion paths to accelerate redox reactions. These confer Ni2P/NC@CoNi2S4 with a high specific capacitance of 2499 F·g-1 at 1 A·g-1. The NiCo-LDH template producing a tight interfacial connection, significantly enhances the stability of the heterostructure, leading to a 91.89% capacitance retention after 10,000 cycles. Moreover, the fabricated Ni2P/NC@CoNi2S4//NC asymmetric supercapacitor exhibits an excellent energy density of 73.68 Wh kg-1 at a power density of 700 W kg-1, superior to most reported composites of TMPs or TMSs.

Hierarchically porous bone scaffold fabricated via direct foam writing with TCP/ZrO2 composite ink

Customizing bone scaffolds to mimic the hierarchically porous structure of natural bone presents a promising strategy for treating critical bone defects. Although low-cost direct ink writing (DIW) is often used to customize bone scaffolds, the limited print resolution made it difficult to print microporous structures. In this study, DIW was combined with the direct foam method to construct bone scaffolds with hierarchical and interconnected macro-micro porous structures. The foam stabilization mechanism of pure TCP was investigated to prepare TCP-enhanced ZrO2-based composite foam inks. Incorporating TCP endowed a richer interconnection structure to the composite foam. The printed bone scaffolds feature three scales of pore structure: interconnected macropores of 400–500 μm, bubble template pores of 50 μm, and open pores of <20 μm. The scaffold exhibited properties comparable to cancellous bone, such as 90 % porosity, 3.1 MPa compressive strength, and 1.0 GPa elastic modulus. In vitro experiments have demonstrated that cells can grow into the interior of the scaffold by following the connecting pores. And, incorporating TCP significantly enhances osteogenic protein and gene expression in bionic bone scaffolds. This facile and controllable approach offers an alternative solution to addressing the challenge of clinical implant shortages.

Superspreading Surface with Hierarchical Porous Structure for Highly Efficient Vapor-Liquid Phase Change Heat Dissipation.

Superspreading surfaces with excellent water transport efficiency are highly desirable for addressing thermal failures through the liquid-vapor phase change of water in electronics thermal management applications. However, the trade-off between capillary pressure and viscous resistance in traditional superspreading surfaces with micro/ nanostructures poses a longstanding challenge in the development of superspreading surfaces with high cooling efficiency in confined spaces. Herein, a heat-treated hierarchical porous enhanced superspreading surface (HTHP) for highly efficient electronic cooling is proposed. Compared with the single porous structures in nanograss, nanosheets, and copper foam, HTHP with hierarchical honeycomb pores effectively resolves the trade-off effect by introducing large vertical through-pores to reduce viscous resistance, and connected small pores to provide sufficient capillary pressure synergistically. HTHP exhibits excellent capillary performance in both horizontal spreading and vertical rising. Despite a thickness of only 0.33mm, the as-prepared ultrathin vapor chamber (UTVC) fabricated to exploit the superior capillary performance of HTHP achieved effective heat dissipation with outstanding thermal conductivity (12121 Wm-1K-1), and low thermal resistance (0.1 KW-1) at a power of 5W. This regulation strategy based on hierarchical honeycomb porous structures is expected to promote the development of high-performance superspreading surfaces with a wide range of applications in thermal management.

Simulation of Hydrogen Adsorption in Hierarchical Silicalite: Role of Electrostatics and Surface Chemistry.

Adsorption in nanoporous materials is one strategy that can be used to store hydrogen at conditions of temperature and pressure that are economically viable. Adsorption capacity of nanoporous materials depends on surface area which can be enhanced by incorporating a hierarchical pore structure. We report grand canonical Monte Carlo (GCMC) simulation results on the adsorption of hydrogen in hierarchical models of silicalite that incorporate 4 nm wide mesopores in addition to the 0.5 nm wide micropores at 298 K, using different force fields to model hydrogen. Our results suggest that incorporating mesopores in silicalite can enhance adsorption by at least 20 % if electrostatic interactions are not included and up to 100 % otherwise. Incorporating electrostatic interactions results in higher adsorption by close to 100 % at lower pressures for hierarchical silicalite whereas for unmodified silicalite, it is less significant at all pressures. Hydroxylating the mesopore surface in hierarchical silicalite results in an enhancement in adsorption at pressures below 1 atm and suppression by up to 20 % at higher pressures. Temperature dependence at selected pressures exhibits expected decrease in adsorption amounts at higher temperatures. These findings can be useful in the engineering, selection, and optimization of nanoporous materials for hydrogen storage.

Lightweight, Elastic, and Superhydrophobic Multifunctional Organic-Inorganic Fibrous Aerogels for Efficient Oily Wastewater Purification and Electromagnetic Microwave Absorption.

Lightweight and robust aerogels with multifunctionality are highly desirable to meet the technological demands of current society. Herein, we designed lightweight, elastic, and superhydrophobic multifunctional organic-inorganic fibrous hybrid aerogels which were assembled with organic aramid nanofibers and inorganic hierarchical porous carbon fibers. Thanks to the organic-inorganic fiber hybridization strategy, the optimal aerogels possessed remarkable compressibility and elasticity. Benefiting from the microscopic hierarchical porous structure of carbon fibers and the macroscopic macroporous lamellar structure of aerogels, the optimal aerogels exhibited superb lightweight property, conspicuous electromagnetic microwave absorption ability, and outstanding oily wastewater purification capacity. As for electromagnetic microwave absorption, it achieved a strong reflection loss of -41.8 dB, and the effective absorption bandwidth reached 6.86 GHz. Besides, the oil adsorption capacity for trichloromethane reached as high as 93.167 g g-1 with a capacity retention of 95.6% after 5 cycles. Meanwhile, it could act as a gravity-driven separation membrane to continuously separate trichloromethane from a trichloromethane-water mixture with a high flux of 7867.37 L·m-2·h-1, even for surfactant-stabilized water-in-n-heptane emulsions of 3794.94 L·m-2·h-1. Such a strategy might shed some light on the construction of multifunctional aerogels toward broader applications.

Towards 3D Pore Structure of Porous Gypsum Cement Pozzolan Ternary Binder by Micro-Computed Tomography

A sophisticated characterisation of a porous material structure has been challenging in material science. Three-dimensional (3D) structure analysis allows the evaluation of a material’s homogeneity, pore size distribution and pore wall properties. Micro-computed tomography (micro-CT) offers a non-destructive test method for material evaluation. This paper characterises a novel ternary binder’s porous structure using micro-CT. Gypsum–cement–pozzolan (GCP) ternary binders are low-carbon footprint binders. Both natural and industrial gypsum were evaluated as a major components of GCP binders. Porous GCP binder was obtained by a foaming admixture, and the bulk density of the material characterised ranged from 387 to 700 kg/m3. Micro-CT results indicate that pores in the range from 0.017 to 3.0 mm can be effectively detected and described for porous GCP binders. The GCP binder structure proved to be dominant by 0.1 to 0.2 mm micropores. For GCP binders produced with natural gypsum, macropores from 2.2 to 2.9 mm are formed, while GCP binders with phosphogypsum possess pores from 0.2 to 0.6 mm. Micro-CT proved to be an effective instrument for characterising the homogeneity and hierarchical pore structure of porous ternary binders.

Hydrogen-bonded micelle assembly directed conjugated microporous polymers for nanospherical carbon frameworks towards dual-ion capacitors

Well-orchestrated carbon nanostructure with superb stable framework and high surface accessibility is crucial for zinc-ion hybrid capacitors (ZIHCs). Herein, a hydrogen-bonded micelle self-assembly strategy is proposed for morphology-controllable synthesis of conjugated microporous polymers (CMPs) derived carbon to boost zinc ion storage capability. In the strategy, F127 micellar assembly through intermolecular hydrogen bonds serves as structure-directed agents, directing CMPs’ oligomers grow into nanospherical assembly. The nanospherical carbon frameworks derived from CMPs (CNS-2) have shown maximized surface accessibility due to their plentiful tunable porosity and hierarchical porous structure with abundant mesoporous interconnected channels, and superb stability originating from CMPs’ robust framework, thus the CNS-2-based ZIHCs exhibit ultrahigh energy density of 163 Wh kg−1 and ultralong lifespan with 93 % capacity retention after 200, 000 cycles at 20 A g−1. Charged ion storage efficiency also lies in dual-ion alternate uptake of Zn2+ and CF3SO3− as well as chemical redox of Zn2+ with carbonyl/pyridine motifs forming O–Zn–N bonds. Maximized surface accessibility and dual-ion storage mechanism ensure excellent electrochemical performance. Thus, the hydrogen-bond-guide micelle self-assembly strategy has provided a facile way to design nanoarchitectures of CMPs derived carbon for advanced cathodes of ZIHCs.

Design of High-Performance Formyl-Functionalized COF Aerogels as Quasi-Solid Lithium Battery Electrolyte by a Solvent Substitution Strategy.

Covalent organic framework (COF) aerogels with functional groups offer exceptional processability and functionality for various applications. These hierarchical porous materials combine the advantages of COFs with the benefits of aerogels, overcoming the limitations of conventional insoluble and nonfusible COF powders. However, achieving both high crystallinity and shape retention remains a challenge for functionalized COF aerogels. In this work, we develop a novel and general solvent substitution method for the one-step synthesis of formyl-functionalized COF aerogels without harsh vacuum conditions. These aerogels exhibit excellent processing capabilities, superior mechanical strength, and enhanced functionality. As a proof-of-concept, they were used in adsorption and lithium metal battery applications, significantly maximizing the structural advantages of COFs, e.g.: (i) the hierarchical porous structure is fully wetted by the electrolyte to form continuous transport channels; (ii) the polar groups, which are easier to be acquired, help in desolvation and transfer of Li+; (iii) the regular pore structures stabilize deposition of Li+ and inhibit the growth of lithium dendrites. These combined benefits contribute to a lighter battery with improved energy density and enhanced safety.

Micro-mesoporous carbons form non-porous zinc-organic coordination compounds: Synthesis, structure and gas adsorption properties

A series of non-porous zinc-containing coordination compounds with mono- and polydentate ligands has been used to produce carbon materials with a hierarchical porous structure. Adjustment of the carbonization mode enables to increase the target product yield by an average of three times. The obtained carbons have a combination of micro- and mesopores with a pronounced maximum at 3.5 nm. The gas-sorption behavior of the obtained carbons has been studied over a wide range of temperatures and pressures. It has been established that the amount of excess adsorption for hydrogen and methane reaches 2.7 and 15 wt%, respectively. The extension of the proposed approach to the use of simple bimetallic complexes as precursors may be promising for obtaining effective catalysts based on a carbon matrix with controlled porosity and encapsulated nanoscale particles of a catalytically active metal.

Basic magnesium carbonate template assisted co-carbonization of potassium citrate toward hierarchical porous carbon for supercapacitors

Hierarchical porous carbon (HPC) as the ideal host material for supercapacitors has received extensive attention. However, traditional methods of fabricating HPC often rely on organic macromolecules and complex procedures. Herein, a simple and straightforward approach is developed for the synthesis of HPC through basic magnesium carbonate template assisted co-carbonization of potassium citrate. Potassium citrate can be effectively embedded and encapsulated with basic magnesium carbonate due to the large bulk density difference between them. In the pyrolysis process, the carbon-containing small molecules produced by the pyrolysis of potassium citrate are deposited on the surface of MgO surface obtained from the decomposition of basic magnesium carbonate, and the etching reaction of potassium salt, CO2 and primary carbon structure occurs. The competitive rate of carbon deposition reaction and etching reaction can be easily controlled by changing the ratio of potassium citrate and basic magnesium carbonate. The obtained carbon materials show the morphology changes of nanoparticle accumulations, discontinuous carbon frames and carbon planar blocks, and the hierarchical porous structure of carbon materials can also be controlled in a wide range. HPC-2 exhibits the morphology of nanoparticle accumulation and generates abundant meso-macropores, which accelerates the rapid transport of electrolytic ions. The micropores inside the nanoparticles provide an accessible room for ionic adsorption. Benefited from this unique microstructural framework, HPC-2 shares a high capacitance of 305.5 F g−1 at 0.5 A g−1 and 173.1 F g−1 at 50 A g−1. Furthermore, the assembled symmetric supercapacitors exhibit a high energy density and power density than YP-50 F throughout the test range. The versatility of this synthetic strategy provides an insight into directional tailoring fine pore structure and micro-morphology of carbon materials based on small molecule deposition.

Synthesis and mechanism of hierarchical porous Ag/CuxO (x = 1, 2) nanowire hybrids for high photocatalytic degradation

To improve organic pollutant degradation ability, this work aims at designing a novel porous Cu-Ag bimetal hybrid with unique architecture, fertile porosity as well as Schottky junction. Herein, a free-standing hybrid with Ag nanoparticles modified CuxO (x = 1, 2) nanowires in-situ grown on the nanoporous Cu-Ag bimetal network (Ag/CuxO@NP-CuAg) was successfully synthesized by dealloying and then anodizing process. Compared with monometallic CuxO nanowires integrated with nanoporous Cu substrate (CuxO@NPC), the Ag/CuxO@NP-CuAg hybrids with the Ag/CuxO Schottky junction and SPR effect of Ag nanoparticles, are favorable to accelerate the transportation of photo-generated carriers and avoid the recombination of electrons (e-) and holes (h+), thus exhibiting the enhanced photocatalytic performance for RhB. Such remarkable performance is also contributed to the multimodal hierarchical porous structure and the integration design strategy. Moreover, by density functional theory (DFT) calculation, a typical Z-scheme mechanism is proposed to better understand the photocatalytic degradation process. The formation mechanism of the Ag/CuxO nanowires is also investigated.

N/S‐Doped Hierarchical Porous Bamboo Carbon Fibers with Ultra‐Large Surface Area and Highly Exposed Active Sites for Flexible Zinc‐Air Battery†

Comprehensive SummaryFacile mass transport channel and accessible active sites are crucial for binder‐free air electrode catalysts in rechargeable flexible zinc‐air battery (ZAB). Herein, a ZnS/NH3 dual‐assisted pyrolysis strategy is proposed to prepare N/S‐doped hierarchical porous bamboo carbon cloth (HP‐NS‐BCC) as binder‐free air electrode catalyst for ZAB. BCC fabric with abundant micropores is firstly used as flexible carbon support to facilitate the heteroatom‐doping and construct the hierarchical porous structure. ZnS nanospheres and NH3 activization together facilitate the electronic modulation of carbon matrix by N/S‐doping and optimize the macro/meso/micropores structure of carbon fibers. Benefiting from the highly‐exposed N/S‐induced sites with enhanced intrinsic activity, the optimized mass transport of biocarbon fibers, as well as the ultra‐large specific surface area of 2436.1 m2·g–1, the resultant HP‐NS‐BCC catalyst exhibits improved kinetics for oxygen reduction/evolution reaction. When applied to rechargeable aqueous ZABs, it achieves a significant peak power density of 249.1 mW·cm−2. As binder‐free air electrode catalyst, the flexible ZAB also displays stable cycling over 500 cycles with a minimal voltage gap of 0.42 V, showcasing promising applications in flexible electronic devices.

Wood flour and kraft lignin enable air-drying of the nanocellulose-based 3D-printed structures

The predominant technique for producing 3D-printed structures of nanocellulose involves freeze-drying despite its drawbacks in terms of energy consumption and carbon footprint. This study explores the less-energy-intensive drying approach by leveraging the valorization of forest residual streams. We utilized wood flour and Kraft lignin as fillers to facilitate room-temperature drying of the nanocellulose-based 3D printed structures. Various ink formulations, integrating cellulose nanofibers, wood flour, and lignin, were tested for direct ink writing (DIW). The formulations exhibited shear-thinning behavior and distinct yield stress with rising stress levels, ensuring the effective flow of the ink during DIW. Consequently, multilayered objects were printed with high shape fidelity and precise dimensions. Lignin and wood flour prevented structural collapse upon room-temperature drying. A reduced shrinkage was observed with the addition of lignin in freeze and room temperature drying. Moreover, the room-temperature dried samples were denser and demonstrated significantly higher resistance to applied compressive force, surpassing those reported for cellulose-based 3D composites in the existing literature. Remarkably, the trade-off effects of lignin are highlighted in terms of efficient stress-distributing and micro-scale sliding, enabling better strength. Along with wood flour, it further increases thermal stability. However, lignin hinders the hierarchical porous structure, the main ion transportation channels, reducing the double-layer capacitance of the carbonized structures. Overall, the results underscore the potential of all-biobased formulations for DIW for practical applications, highlighting their enhanced mechanical properties and structural integrity via the more sustainable drying method.

Hybrid Molecular Sieve-Based Interfacial Layer with Physical Confinement and Desolvation Effect for Dendrite-free Zinc Metal Anodes.

The side reactions and dendrite growth at the interface of Zn anodes greatly limit their practical applications in Zn metal batteries. Herein, we propose a hybrid molecular sieve-based interfacial layer (denoted as Z7M3) with a hierarchical porous structure for Zn metal anodes, which contains 70 vol % microporous ZSM-5 molecular sieves and 30 vol % mesoporous MCM-41 molecular sieves. Through comprehensive molecular dynamics simulations, we demonstrate that the mesopores (∼2.5 nm) of MCM-41 can limit the disordered diffusion of free water molecules and increase the wettability of the interfacial layer toward aqueous electrolytes. In addition, the micropores (∼0.56 nm) of ZSM-5 can optimize the Zn2+ solvation structures by reducing the bonded water molecules, which simultaneously decrease the constraint force of solvated water molecules to Zn2+ ions, thus promoting the penetrability and diffusion kinetics of Zn2+ ions in Z7M3. The synergetic effects from the hybrid molecular sieves maintain a constant Zn2+ concentration on the surface of the Zn electrode during Zn deposition, contributing to dendrite-free Zn anodes. Consequently, Z7M3-coated Zn electrodes achieved excellent cycling stability in both half and full cells.

Femtosecond laser-enabled facile tuning of Cu selectivity towards long-chain products in CO2 electroreduction

In the quest to mitigate excessive CO2 emissions, the electrochemical reduction of CO2 (eCO2R) into multi-carbon fuels and vital chemical precursors emerges as a compelling strategy. Meticulous control of the C–C coupling on a catalyst surface is a grand challenge in the selective production of desired C2+ products. Ethane and propanol are among the most desirable C2+ products in the gas and liquid phase, respectively. Herein, we demonstrate facile femtosecond laser-enabled tuning of Cu selectivity towards ethane and propanol. The laser-enabled tailoring of the Cu surface induces a shift from C1 products to ethane and propanol. This shift in product composition is attributed to the concurrent creation of hierarchical porous structures, the stabilization of {111}, {200}, and {220} Cu2O facets, and the promotion of the Cu1+ oxidation state. These alterations collectively enhance the adsorption strength, leading to an increased propensity for C-C coupling and, consequently, an elevated selectivity toward C2+ products.