Chemical Dealloying Research Articles

Nanoporous Cu-based amorphous alloys prepared by selective dissolution in acidic media

Abstract Functional nanoporous materials are considered a significant category of nanostructured materials that exhibit distinct characteristics like high surface area, porosity, and improved mass transport properties. These qualities render them suitable for a wide range of applications including catalysis, energy storage, biomedical fields, and electrochemical sensors. Dealloying or laser-induced technologies are the primary methods employed to fabricate such nanoporous materials. Dealloying is a dependable top-down approach used to produce hierarchical, disordered nanoporous materials with customizable pore sizes in the range of a few nanometers. The process of dealloying involves the selective elimination or dissolution of one or more elements from an alloy through a corrosion mechanism, using various dealloying techniques, such as chemical, electrochemical, liquid metal, or vapor phase dealloying. In the present study, copper-based amorphous metallic ribbons (Cu75Ni6Sn5P10Ga4) were initially manufactured using the melt-spinning method. The Cu-based amorphous ribbons were structurally investigated by X-ray diffraction and thermal analysis. Subsequently, the ribbons were subjected to a dealloying treatment, using an acidic solution to selectively dissolve the nickel from their composition and to obtain a nanoporous structure. The microstructure and chemical composition of the ribbons before and after the dealloying process were investigated using scanning electron microscopy (SEM), combined with energy-dispersive X-ray spectroscopy. The dealloying process performed in 1 M H2SO4 solution at 25 °C for 60 minutes leads to a large number of nanopores, uniformly distributed onto the surface of the Cu-based ribbons.

Advanced multi-component FeCoCuAlMo intermetallic electrocatalysts for efficient and sustainable hydrogen evolution in alkaline freshwater and seawater

Electrolyzing seawater to produce hydrogen is a promising sustainable energy production technology. The current non-precious metal-based hydrogen evolution reaction (HER) electrocatalysts demonstrate inadequate catalytic activity and poor stability in seawater electrolyte. Therefore, developing stable and efficient non-precious metal-based HER electrocatalysts is a major challenge for achieving sustainable green energy development. This work reports a multi-component intermetallic catalyst FeCoCuAlMo prepared by arc melting and chemical dealloying methods. The electrocatalytic hydrogen evolution performance of catalysts with varying atomic ratios (FeCoCu)20(Al70Mo30)80, (FeCoCu)30(Al70Mo30)70, (FeCoCu)40(Al70Mo30)60, and (FeCoCu)50(Al70Mo30)50 in alkaline seawater and alkaline electrolyte was studied. The findings indicate that these catalysts primarily consist of AlMo3 and (Cu0.35Fe0.35Co0.3)Al, among which the dealloyed (FeCoCu)30(Al70Mo30)70 exhibits excellent catalytic activity with overpotentials of 137.54 and 116.91 mV at a current density of 100 mA/cm2 in alkaline seawater and alkaline electrolyte, respectively, outperforming most catalysts. Additionally, it demonstrated long-term stability in alkaline seawater and alkaline electrolyte for 250 and 400 h without significant decay at overpotentials of 236 mV and 276 mV, respectively. This improved performance can be attributed to the unique structure of the multi-component intermetallic compound, which provides good thermodynamic stability and synergistic effects among its constituents, thereby enhancing HER performance. Within this multi-component intermetallic compound, AlMo3 particles serve as the primary conductive medium to accelerate electron transfer, while (Cu0.35Fe0.35Co0.3)Al serves as the main active site, resulting in a stable structure that provides the catalyst with high catalytic activity and good stability. Thus, the (FeCoCu)30(Al70Mo30)70 electrocatalyst is a promising candidate for seawater electrolysis aimed at hydrogen production.

Unraveling the dealloying mechanism of a Au33Fe67 metastable precursor for a low-cost nanoporous gold production

A low-cost Nanoporous Gold (NPG) has been successfully prepared by chemical dealloying of a Au33Fe67 supersaturated solid solution, whose ribbons were obtained by rapid solidification using melt-spinning technique. The dealloying procedures were carried out in 1 M HNO3 at 70 °C for varying durations. As-quenched ribbon and dealloyed samples have been structurally and compositionally investigated using XRD, FESEM and EDS techniques. The obtained NPG is homogeneous with tunable ligament size and shape, easy-to-handle and free-standing. Most notably, a metastable precursor has been favourably obtained from an immiscible Au-Fe system. Furthermore, according to the characterization results, a mechanism of dealloying has been proposed. Pairing Au with cheap and abundant Fe and fabricating an Fe-rich precursor gives an exceedingly cost-effective starting material. No usage of critical raw materials is involved. Then, employing a straight-forward and rapid dealloying procedure to obtain the NPG sample, makes for an overall inexpensive and sustainable production.

Three-dimensional nanoporous gold/gold nanoparticles substrate for surface-enhanced Raman scattering detection of illegal additives in food

Owing to their nanoscale size and porous structure, both colloidal gold nanoparticles (AuNPs) and nanoporous gold (NPG) have demonstrated good and stable surface-enhanced Raman scattering (SERS) activity, and are therefore widely used as SERS substrates for the rapid detection of various components in food, environmental, biological, and other samples. In this study, we fabricated a novel, sensitive, and reproducible composite three-dimensional (3D) substrate for rapid SERS-based detection of illegal additives in food products. AuNPs and NPGs were prepared by chemical reduction and chemical dealloying methods, with the particle size of AuNPs about 60 nm and the pore size of NPG in the range of 5–36 nm. The AuNPs were then assembled on the surface of NPG to form the composite substrate 3D-NPG/AuNPs, which was characterized by transmission electron microscopy, scanning electron microscopy, X-ray diffraction, and other methods. Finally, the new SERS substrate combined with a portable Raman spectrometer was used to detect the illegal food additives 6-benzylaminopurine and melamine, with detection limits of 1 × 10−9 M and 5 × 10−7 M respectively. We further analyzed the relationship between the dealloying time-controlled morphology and the SERS properties of NPG, demonstrating that 3D-NPG/AuNPs as a novel SERS substrate have strong practical application potential in the rapid detection of food additives and other substances.

Nanoporous Gold Thin Films as Substrates to Analyze Liquids by Cryo-atom Probe Tomography.

Cryogenic atom probe tomography (cryo-APT) is being developed to enable nanoscale compositional analyses of frozen liquids. Yet, the availability of readily available substrates that allow for the fixation of liquids while providing sufficient strength to their interface is still an issue. Here, we propose the use of 1-2-µm-thick binary alloy film of gold-silver sputtered onto flat silicon, with sufficient adhesion without an additional layer. Through chemical dealloying, we successfully fabricate a nanoporous substrate, with an open-pore structure, which is mounted on a microarray of Si posts by lift-out in the focused-ion beam system, allowing for cryogenic fixation of liquids. We present cryo-APT results obtained after cryogenic sharpening, vacuum cryo-transfer, and analysis of pure water on the top and inside the nanoporous film. We demonstrate that this new substrate has the requisite characteristics for facilitating cryo-APT of frozen liquids, with a relatively lower volume of precious metals. This complete workflow represents an improved approach for frozen liquid analysis, from preparation of the films to the successful fixation of the liquid in the porous network, to cryo-APT.

Flexible SERS substrates with gradient porous Cu structure dealloying from the thermal diffusion couples of Al/Cu stacking foils

Accurate and sensitive surface-enhanced Raman scattering (SERS) substrates are urgently demanded for the various analytic techniques. The SERS substrates with multimodal and gradient porous structure, utilized for the Rhodamine 6G (R6G) detection, have been designed and successfully fabricated from the thermal diffusion couples of Al and Cu foils via chemical dealloying. The structural inheritance of the initial microstructure of thermal diffusion couple precursors governs the formation of the final layer-by-layer gradient porous Cu with different characteristic pore sizes and morphology. An outmost surface layer of disordered lipstick-like porous structure on the SERS substrates enhances SERS effects as has been expected. The SERS activity of R6G Raman probes on gradient porous Cu is evaluated as a SERS enhancement factor of 6.63 × 1012 and limit of detection of 2.10 × 10−17 mol/L, higher than other porous SERS substrates. Meanwhile, the present SERS substrates are flexible and exhibit good bending properties due to the unreacted Cu layer as a supporting skeleton and other gradient porous Cu layers. The superior SERS performances are considered to result from the synergetic effects of the surface scattering of porous Cu rods and enhancements of the high electromagnetic fields between the small gaps between the nanopores.

Surface activation via selective dealloying of Cu-based metallic glasses for efficient catalytic behavior.

Surface activation is considered to regulate the electronic structures of materials for enhancing catalytic capability. Herein, we report a controllable strategy for constructing three-dimensional micro-nanoporous copper catalysts with high reactivity and activity for the degradation reaction of organic pollutants. Various micro-nanoporous structures and in situ formation processes by chemical selective dealloying of Cu-based metallic glasses are evaluated due to the surface modification. The porous catalysts exhibit superior catalytic performance, attributing to the catalytic mechanisms related to the superior surface activity of nanoscale copper composites and the strong oxidizing capability of activated radicals. These findings will provide a promising synthesis approach for three-dimensional micro-nanoporous catalysts for many chemical reactions.

Scalable substrate development for aqueous sample preparation for atom probe tomography.

Reliable and consistent preparation of atom probe tomography (APT) specimens from aqueous and hydrated biological specimens remains a significant challenge. One particularly difficult process step is the use of a focused ion beam (FIB) instrument for preparing the required needle-shaped specimen, typically involving a "lift-out" procedure of a small sample of material. Here, two alternative substrate designs are introduced that enable using FIB only for sharpening, along with example APT datasets. The first design is a laser-cut FIB-style half-grid close to those used for transmission-electron microscopy, that can be used in a grid holder compatible with APT pucks. The second design is a larger, standalone self-supporting substrate called a "crown," with several specimen positions that self-aligns in APT pucks, prepared by electrical discharge machining (EDM). Both designs are made nanoporous, to provide strength to the liquid-substrate interface, using chemical and vacuum dealloying. We select alpha brass a simple, widely available, lower-cost alternative to previously proposed substrates. We present the resulting designs, APT data, and provide suggestions to help drive wider community adoption. Lay Description Atom probe tomography (APT) maps the composition of solid materials in three dimensions with sub-nanometre resolution. Preparation of specimens from aqueous specimens remains a significant challenge. To aid with preparation, we introduce here two substrate designs that can hold suitable volumes of liquid for freezing, prior to shaping the final specimen into a sharp needle for APT by using cryogenic focused ion beam milling. We also describe the complete setup that we designed for handling these substrates, including dedicated sample holders. Both substrates are made nanoporous, to provide strength to the liquid-substrate interface, using chemical and vacuum dealloying of alpha brass a simple, widely available, low-cost material. We finally showcase APT data and provide suggestions to help drive wider community adoption. This article is protected by copyright. All rights reserved.

Defect-rich hierarchical porous spinel MFe2O4 (M = Ni, Co, Fe, Mn) as high-performance anode for lithium ion batteries

Exploring innovative anode materials with excellent lithium storage capability is an urgent and challenging task. Among various candidates, the spinel ferrites based anodes received huge attention owing to the high theoretical capacity. However, the rapid capacity decaying and sluggish reaction kinetics during cycling have severely hampered their commercialization process. Herein, the hierarchical porous spinel MFe2O4 (M = Ni, Co, Mn, Fe), comprised of Mn doped porous NiFe2O4/CoFe2O4 heterostructure ligament network and Ni/Co/Mn co-doped Fe3O4 nanosheets network, is synthesized through a facile chemical dealloying strategy. The as-prepared MFe2O4 anode shows impressive cycling stability, revealing a discharge capacity of 1161.6 mAh g−1 after cycling for 1500 cycles at 500 mA g−1. Furthermore, the assembled LiFePO4//MFe2O4 full cell can display a reversible capacity of 111.2 mAh g−1 at 0.5 C after 150 cycles, exhibiting the great potential of the practical application of the MFe2O4 in the next-generation LIBs. The remarkable Li storage properties can be attributed to the particular hierarchical porous structure, highly active NiFe2O4/CoFe2O4 heterointerface and abundant surficial oxygen defects, high stable spinel structure contributed from high conformational entropy of polymetallic ions, and a double role of Mn doping in the cycling process. The structure regulating strategy proposed here is greatly expected to boost the developing of high-performance spinel ferrites based anodes.

Enhancing the chemoselective hydrogenation of o-chloronitrobenzene over nanoporous Ni/NiAl3 catalysts

Halogenated aniline, which is usually produced by hydrogenation of halogenated nitrobenzene, is extensively employed in a variety of fields, including insecticides, medicines, pigments, and cosmetics. The design of catalysts to increase their selectivity in this application has become one of the research objectives. Herein, the nanoporous Ni/NiAl3 catalysts with a high specific surface area were designed and prepared by chemical dealloying of NiAl alloy, and the thickness of surface Ni could be easily adjusted. In the hydrogenation of o-chloronitrobenzene (o-CNB) to o-chloroaniline (o-CAN), the catalyst demonstrated great catalytic activity (TOF up to 155 h−1), the TOF is three times that of Raney Ni, and the selectivity to o-CAN remained over 99 % at complete conversion under 50 °C and 2 MPa of H2. The findings demonstrate that at low surface Ni thickness, NiAl3 and Ni have a synergistic effect that alters the electron cloud density of the active site in a way that strengthens the adsorption of intermediates and can successfully modulate selectivity while maintaining high activity. These provide the foundation for designing high selectivity catalysts and preparing nanoporous intermetallic compound catalysts.

Multinary intermetallic with enhanced catalytic activity and prolonged stability at high current density for electrochemical hydrogen production

Developing robust and efficient nonprecious metal-based electrocatalysts toward hydrogen evolution reaction (HER) is a big challenge for green and sustainable energy since insufficient catalytic activity and poor stability of current catalysts cannot meet the application requirements. This work reports a freestanding HER electrode FeNiCuAlMo prepared by arc-melting and chemical dealloying methods. The HER performance firstly improves and then declines with the increase of dealloying time. When the dealloying time is 3 h, the electrode shows optimal catalytic performance. The fabricated electrode is composed of AlMo3 and Al5CuMo2, where micro-sized AlMo3 particles are embedded in cellular dendritic Al5CuMo2. Impressively, it displays excellent HER performance, including a small overpotential of 173 mV at a current density of 500 mA/cm2 and outstanding long-term stability for 100 h of continuous hydrogen evolution at 1000 mA/cm2 in an alkaline electrolyte without obvious attenuation. The intrinsic activity of the electrodes combined intermetallic compounds with hierarchical porous structure provides several effects, including enhanced massive active sites, electrolyte access, electron transport, and fast gas release that contribute jointly to enhancing HER activities. The micro-sized AlMo3 particles provide robust framework for the dendritic Al5CuMo2 active sites center, allowing the exposure of enough active sites and simultaneously maintaining good stability. The highly stable and active electrocatalytic HER property makes it as a promising candidate for practical hydrogen production.

Chemical-Dealloying-Derived PtPdPb-Based Multimetallic Nanoparticles: Dimethyl Ether Electrocatalysis and Fuel Cell Application.

In this work, we report a novel multimetallic nanoparticle catalyst composed of Pt, Pd, and Pb and its electrochemical activity toward dimethyl ether (DME) oxidation in liquid electrolyte and polymer electrolyte fuel cells. Chemical dealloying of the catalyst with the lowest platinum-group metal (PGM) content, Pt2PdPb2/C, was conducted using HNO3 to tune the catalyst activity. Comprehensive characterization of the chemical-dealloying-derived catalyst nanoparticles unambiguously showed that the acid treatment removed 50% Pb from the nanoparticles with an insignificant effect on the PGM metals and led to the formation of smaller-sized nanoparticles. Electrochemical studies showed that Pb dissolution led to structural changes in the original catalysts. Chemical-dealloying-derived catalyst nanoparticles made of multiple phases (Pt, Pt3Pb, PtPb) provided one of the highest PGM-normalized power densities of 118 mW mgPGM-1 in a single direct DME fuel cell operated at low anode catalyst loading (1 mgPGM cm-2) at 70 °C. A possible DME oxidation pathway for these multimetallic catalysts was proposed based on an online mass spectrometry study and the analysis of the reaction products.

Mechanically enhancing a brazed joint of WC-Co/3Cr13 by utilizing a nanoporous Cu lamina interlayer prepared by chemical dealloying

Ag-Cu-Ti brazing alloys may allow sound joining between WC-Co cemented carbide (YG20) and 3Cr13 stainless steel. However, the issue of excessive formation of agglomerated brittle Cu-Ti compounds in the joint seam, which deteriorates mechanical performance, is still a major processing drawback. Here, a nanoporous copper (NP-Cu) lamina, prepared by chemically dealloying an Mg67Cu33 (at. %) alloy precursor, was used as an interlayer for assisting the brazing process between YG20 alloy and 3Cr13 stainless steel. The effect of introducing the NP-Cu interlayer on the microstructure and mechanical properties of the joints was investigated. Results revealed that the Cu-Ti compounds in the brazing seam acquired reduced size and dispersed distribution by applying the NP-Cu interlayer. The technique outperforms the directly brazed alternative, with a shear strength increase of 70%. The interlayer contributed by its high specific surface and excellent surface metallurgical activity, overcoming the drawback of agglomerated Cu-Ti compound development. The new technique allows a process based microstructural and chemical control, with vast potential applications in the joining of WC-Co cemented carbide and stainless-steel materials.

Nanoporous Cu-based metamaterial for fenton-like catalysis

Nanoporous metals are considered as the ideal catalysts owing to their open pore structure and high surface area. In the present work, a series of nanoporous Cu-based metamaterial (nano-Cu/MM) catalysts with triply periodic minimal surface (TPMS) were developed by the selective laser melting (SLM) and chemical dealloying process. The TPMS structure endowed the porous metamaterial with an excellent mechanical property and an abundant pathway for mass transfer. The as-prepared nano-Cu/MM was applied as a Fenton-like catalyst in the advanced oxidation process, and the degradation rate of methylene blue (MB) was as high as 99 % in 10 min. In addition, the catalyst showed a good applicability, which could effectively degrade the complex dyes and tetracycline drugs. To meet the practical application, a TPMS-structured coaxial circular with nanoporous structure was designed and prepared by the same process, which could be simply assembled with an electric motor to achieve a continuous catalytic degradation, demonstrating its potential for the industrial applications.

Fabrication of Superhydrophobic Porous Brass by Chemical Dealloying for Efficient Emulsion Separation.

By taking advantage of typical dealloying and subsequent aging methods, a novel homogeneous porous brass with a micro/nano hierarchical structure was prepared without any chemical modification. The treatment of commercial brass with hot concentrated HCl solution caused preferential etching of Zn from Cu62Zn38 alloy foil, leaving a microporous skeleton with an average tortuous channel size of 1.6 μm for liquid transfer. After storage in the atmosphere for 7 days, the wettability of the dealloyed brass changed from superhydrophilic to superhydrophobic with a contact angle > 156° and sliding angle < 7°. The aging treatment enhanced the hydrophobicity of the brass by the formation of Cu2O on the surface. By virtue of the opposite wettability to water and oil, the aged brass separated surfactant-stabilized water-in-oil emulsions with separation efficiency of over 99.4% and permeate flux of about 851 L·m-2·h-1 even after recycling for 60 times. After 10 times of tape peeling or sandpaper abrasion, the aged brass maintained its superhydrophobicity, indicating its excellent mechanical stability. Moreover, the aged brass still retained its superhydrophobicity after exposure to high temperatures or corrosive solutions, displaying high resistance to extreme environments. The reason may be that the bicontinuous porous structure throughout the whole foil endows stable mechanical properties to tolerate extreme environments. This method should have a promising future in expanding the applications of alloys.

High Areal Capacity, Long Cycle Life Li-Air Batteries Enabled by Nano/Micro Hierarchical Porous Cathode.

The limited cycle life of Li-air batteries (LABs) with high areal capacity remains the chief challenge that hinders their practical applications. Here, the study proposes a hierarchical porous electrode (HPE) design strategy, in which porous MnO nanoflowers are built into mesopore/macropore electrodes through a combination of chemical dealloying and physical de-templating procedures. The MnO nanoflowers with 10-30nm pore provides active sites to catalyze the O2 reduction and decomposition of discharged products. The 5-10µm macroscopic pores in the cathode serve as channels of O2 transportation and facilitate the electrolyte permeation. The proposed HPE exhibits a full discharge capacity of 17.49mAhcm-2 and stable cycle life >2000h with a limited capacity of 6mAhcm-2 . These results suggest that the HPE design strategy for LABs can simultaneously provide large capacity and robust cycle life, which is promising for advanced metal-air batteries.

Nanoporous NiBi catalyst for efficient electrochemical N2 fixation

Electrochemical nitrogen reduction reaction (NRR) in ambient condition provides a sustainable avenue for large-scale NH3 production. However, the development of effective and durable NRR catalysts to promote NH3 synthesis rate and Faraday efficiency (FE) remains a challenge due to the inertness of the N≡N bond. Herein, porous NiBi catalysts which provides abunant active sites were prepared by chemical dealloying of the precursor. Combining theoretical calculations and experimental verification, it is demonstrated that the synergistic effect of Ni and NiBi facilitates the adsorption of N2, inhibits the competition reaction, and reduces the free energy of intermediates (*NNH). Porous Ni91.5Bi8.5 exhibits high catalytic activity for NH3 formation with a yield of 18.35 μg h−1 mg−1 and a FE of 51.12% at −0.3 V vs. RHE, outperforming most reported NRR electrocatalysts under ambient conditions. This strategy is an effective and universal technique for synthesizing catalysts that shows great potential in energy conversion applications.

Enhanced Photothermal Steam Generation and Gold Using the Efficiency of Ultralight Gold Foam with Hierarchical Porosity

Controlling the optical properties of metal plasma nanomaterials through structure manipulation has attracted great attention for solar steam generation. However, realizing broadband solar absorption for high-efficiency vapor generation is still challenging. In this work, a free-standing ultralight gold film/foam with a hierarchical porous microstructure and high porosity is obtained through controllably etching a designed cold-rolled (NiCoFeCr)99Au1 high-entropy precursor alloy with a unique grain texture. During chemical dealloying, the high-entropy precursor went through anisotropic contraction, resulting in a larger surface area compared with that from the Cu99Au1 precursor although the volume shrinkage is similar (over 85%), which is beneficial for the photothermal conversion. The low Au content also results in a special hierarchical lamellar microstructure with both micropores and nanopores within each lamella, which significantly broadens the optical absorption range and makes the optical absorption of the porous film reach 71.1-94.6% between 250 and 2500 nm. In addition, the free-standing nanoporous gold film has excellent hydrophilicity, with the contact angle reaching zero within 2.2 s. Thus, the 28 h dealloyed nanoporous gold film (NPG-28) exhibits a rapid evaporation rate of seawater under 1 kW m-2 light intensity, reaching 1.53 kg m-2 h-1, and the photothermal conversion efficiency reaches 96.28%. This work demonstrates the enhanced noble metal gold using efficiency and solar thermal conversion efficiency by controlled anisotropic shrinkage and forming a hierarchical porous foam.

Electrochemical Dealloying Preparation and Morphology Evolution of Nanoporous Au with Enhanced SERS Activity

Nanoporous Au (NPG) prepared by dealloying is one of the most used substrates for surface-enhanced Raman scattering (SERS). The morphology tailoring of the NPG to obtain both ultrafine pores and suitable Au/Ag ratio is of great importance for the acquiring of enhanced SERS performance. Compared with the chemical dealloying, the electrochemical dealloying can tailor the NPG to be more flexible by the additional adjustment of dealloying voltage and current. Thus, further understanding on the morphology evolution of NPG during the electrochemical dealloying to obtain enhanced SERS performance is of great importance. In the presented work, the morphology and composition evolution of the NPG film during the electrochemical dealloying was investigated. NPG films with a stable pore diameter of approximately 11 nm as well as diverse compositions were obtained by electrochemical dealloying an Au-Ag alloy film. The prepared NPG film exhibits an enhanced SERS activity with an enhancement factor (EF) of 7.3 × 106 and an excellent detection limit of 10−9 M. This work provides insights into the morphology and composition evolution of the NPG during the electrochemical dealloying process to obtain enhanced SERS performance.

Self‐Standing 3D Hollow Nanoporous SnO2‐Modified CuxO Nanotubes with Nanolamellar Metallic Cu Inwalls: A Facile In Situ Synthesis Protocol toward Enhanced Li Storage Properties

AbstractSnO2 is regarded as a prospective anode material candidate for high energy density lithium‐ion batteries (LIBs). However, rapid structural degradation and low conductivity always bring about poor cycling stability and electrochemical reversibility, becoming critical dilemmas toward its practical application. To address these issues, herein, a facile multi‐step in situ synthesis protocol is developed to tactfully achieve self‐standing 3D hollow nanoporous SnO2‐modified CuxO nanotubes with nanolamellar metallic Cu inwalls (3D‐HNP SnO2/CuxO@n‐Cu) via chemical dealloying, heat treatment, electrochemical replacement, and selective etching. The results show that the unique 3D‐HNP SnO2/CuxO@n‐Cu as a binder‐free integrated anode for LIBs exhibits superior Li storage properties with high initial reversible capacity of 3.34 mAh cm−2 and good cycling stability with 85.6% capacity retention and &gt;99.4% coulombic efficiency after 200 cycles (capacity decay of only 0.002 mAh cm−2 per cycle). This is mainly attributed to the unique 3D hollow nanoporous configuration design composed of interlinked CuxO nanotubes modified by ultrafine SnO2 nanocrystals (4–10 nm) with two‐way mechanical strain cushion and nanolamellar metallic Cu inwalls with boosted electrical conductivity. This work can be expected to offer an original and effective approach for rational design and fabrication of advanced MOx‐based anodes toward high‐performance LIBs.