{"paper_id":"239eba2d-1f56-469f-90dd-1289ec01022c","body_text":"Coordinating Etching Inspired Synthesis of noble-metal-free monodisperse high-entropy oxides hollow nanocubes libraries | Research Square window.SnipcartSettings = { analytics: { enabled: false } }; (function() { var accessVector = localStorage.getItem('access_vector') || ''; window.dataLayer = window.dataLayer || []; if (accessVector) { window.dataLayer.push({ user: { profile: { profileInfo: { snid: accessVector } } } }); } })(); (function(w,d,s,l,i){w[l]=w[l]||[];w[l].push({'gtm.start':new Date().getTime(),event:'gtm.js'});var f=d.getElementsByTagName(s)[0],j=d.createElement(s),dl=l!='dataLayer'?'&l='+l:'';j.async=true;j.src='https://www.googletagmanager.com/gtm.js?id='+i+dl;f.parentNode.insertBefore(j,f);})(window,document,'script','dataLayer','GTM-K279D39R'); Browse Preprints In Review Journals COVID-19 Preprints AJE Video Bytes Research Tools Research Promotion AJE Professional Editing AJE Rubriq About Preprint Platform In Review Editorial Policies Our Team Advisory Board Help Center Sign In Submit a Preprint Cite Share Download PDF Article Coordinating Etching Inspired Synthesis of noble-metal-free monodisperse high-entropy oxides hollow nanocubes libraries Huishan Shang, Yuanting Lei, Lili Zhang, Zhiyi Sun, Ning Zhang, and 6 more This is a preprint; it has not been peer reviewed by a journal. https://doi.org/ 10.21203/rs.3.rs-6092386/v1 This work is licensed under a CC BY 4.0 License Status: Published Journal Publication published 06 Nov, 2025 Read the published version in Nature Communications → Version 1 posted You are reading this latest preprint version Abstract High-entropy oxides (HEOs) consist of multiple principal metal cations and oxygen anions, which enhances compositional versatility and promotes the emergence of atypical properties within oxide materials. Nonetheless, precisely shaping HEOs in hollow nanostructures remains a significant challenge due to the disparate nucleation and growth kinetics of the various metal oxide compositions in HEOs. Herein, we present a general strategy for the versatile synthesis of multicomponent hollow nanocubes HEOs libraries from ternary to octonary. A template-assisted route inspired by coordinating etching was utilized for the synthesis of HEOs hollow nanocubes through meticulous selection of the coordinating etchant and optimization of the reaction conditions. This distinctive approach demonstrates the potential for precisely designing high-quality HEOs hollow nanocubes with diverse compositions at room temperature, which potentially manifest promising prospects for various applications. Physical sciences/Materials science/Materials for energy and catalysis Physical sciences/Materials science/Nanoscale materials Figures Figure 1 Figure 2 Figure 3 Figure 4 Figure 5 Introduction High-entropy oxides (HEOs) are regarded as a solid-solution phase, which can be classified into spinel, rock salt, fluorite, and perovskite structures. 1 , 2 , 3 , 4 , 5 They have emerged as a significant focus of research due to their disordered arrangement, interactions among multiple principal elements, and the promotion of entropy. 6 , 7 , 8 , 9 Moreover, the configurational entropy of high-entropy oxides significantly exceeds that of individual monometallic oxides, suggesting that high-entropy oxides exhibit greater thermodynamic stability than their monometallic counterparts at finite temperatures. 10 , 11 , 12 , 13 The previously reported synthesis methods for HEOs are characterized by prolonged heating durations, elevated temperatures, and substantial energy consumption. For instance, they involve the mixing of metal salts followed by heating to temperatures of 900°C or higher to achieve sintering into a single phase. 14 , 15 However, the high temperatures associated with this process can lead to irregular molten bulk formation, limited adjustability of components, and a propensity for phase separation, which may hinder the accessibility of active sites and impair the catalytic reaction process. 16 , 17 Consequently, there is an urgent need for a novel synthesis strategy that is both rapid and controllable, aimed at minimizing heating duration and temperature while effectively managing morphological characteristics. 18 , 19 The utilization of metal hydroxides as precursors constitutes a common approach for the synthesis of metallic oxides. It has been reported that monocomponent, binary, or even ternary metal hydroxides with various components and morphologies can be fabricated through the solution method. Subsequently, the corresponding metal oxides are obtained via low-temperature heat treatment while retaining the original morphologies of the metal hydroxides. 20 , 21 , 22 , 23 , 24 Nevertheless, the incorporation of five or more metallic elements into metal hydroxide precursors poses a significant challenge due to the complex co-precipitation kinetics arising from the disparate physicochemical properties of different metal cations and standard solubility product constants ( K sp ) of metal hydroxides. 25 Furthermore, in a multiple metal hydroxide precursor system, the precipitation sequence of metal species cannot be solely evaluated by K sp . It may also be influenced by factors such as coordination environments, surface energies, organic additives, and the selection of precipitating agents. These variables complicate the control of nucleation and crystal growth processes, which can further affect the morphology of the resulting products. 20 , 26 Consequently, it is crucial to regulate the co-precipitation process and the morphology of metal hydroxide precursors to achieve the formation of single-phase high-entropy oxides. Morphology is a critical property of catalysts, influencing the mass transfer rate as well as the adsorption and desorption of intermediates and products, thereby exerting a significant impact on catalytic performance. 27 Morphological engineering, particularly with respect to regulating dimensionality and size, has been demonstrated as an effective strategy for enhancing physicochemical properties and introducing novel functionalities in catalysts. 28 In particular, three-dimensional hollow architectures that expose high-density active sites and provide additional channels for ionic transport and solution diffusion can shorten the charge transfer pathway and enhance the interaction between reactants and catalysts, thereby significantly improving catalytic efficiency. 29 , 30 However, the construction of three-dimensional hollow architectures in HEOs is seldom reported. In this study, we present a novel and versatile synthetic method for fabricating hollow nanocube HEOs composed of up to eight metallic elements, by a template-assisted route inspired by coordinating etching. The essence of this distinctive strategy hinges on (1) the preparation of the Cu 2 O nanocube template, (2) the release of hydroxide ions (OH⁻) through coordinating etching reactions between a soft base and a soft acid, (3) the co-precipitation of high-entropy metal hydroxides (HE-OH) onto the nanocube shell, and (4) the thermal treatment of HE-OH precursors. This method is achieved by meticulously controlling the balance between the precipitation rate of metal hydroxides and the synchronous coordinating etching rate towards the soft acid. As a demonstration of the catalytic concept, the quinary NiCoFeCdCr-O exhibits a high rate constant ( k ) of 1.79 min⁻¹ for the hydrogenation of p-nitrophenol. Furthermore, NiCoFeCdCr-O demonstrates exceptional stability over 10 cycles, with conversion rates maintained above 95%. Density functional theory (DFT) simulations reveal that the outstanding performance can be ascribed to a more continuous density of states (DOS) near the Fermi level and a more favorable d-band center in HEOs. Our systematic investigation provides valuable insights for the future design of multi-component catalysts with tailored morphologies. Results Theoretical orientation. The template-assisted route inspired by the coordinating etching strategy can be utilized to synthesize metal high-entropy hydroxide precursors, achieved by carefully balancing the precipitation rate of metal hydroxides with the synchronous coordinating etching rate towards the soft acid. 20 , 31 , 32 , 33 The synthetic route is illustrated in Fig. 1 a, and the general chemical process can be described as follows: Cu 2 O + xS 2 O 3 2- +H 2 O → [Cu 2 (S 2 O 3 2- ) x ] 2-2x +2OH - (1) S 2 O 3 2- +H 2 O ⇌ HS 2 O 3 2- + OH - (2) M x+ + xOH - → M(OH) x (3) Initially, the nanocube Cu 2 O was synthesized to function as a soft acid and the soft base Na 2 S 2 O 3 was adopted as the coordinating etchant. In accordance with Pearson's hard and soft acid-base principle, soft Lewis acids can form stable complexes with soft bases. Consequently, the soft acid characteristic of Cu + within the Cu 2 O nanocubes reacts with the soft base ligand (S 2 O 3 2- ) to form the soluble complex [Cu 2 (S 2 O 3 ) x ] 2−2x (Eq. 1), since the soft-soft interaction of Cu + −S 2 O 3 2- is significantly stronger than the soft-hard interaction of Cu + −O 2- within Cu 2 O nanocubes. Apart from the OH − released during the etching of Cu 2 O, there are certain OH − originated from the hydrolysis of S 2 O 3 2− (Eq. 2). Consequently, the other added metal ions (M x+ ) reacted with OH − and concurrently began to precipitate (Eq. 3). The shell structure M(OH) x (denoted as HE-OH) prefers to form around the etching interface where the local concentration of OH − is maximized. The synchronous chemical reactions delineated herein guarantee that the exterior of the HE-OH shell precisely replicates the geometry of the Cu 2 O nanocubes. An alkaline environment is crucial for the co-deposition of multi-metal ions to form metal hydroxides. In this system, the control of the quantities and ratios of Cu 2 O and Na 2 S 2 O 3 exerts a substantial impact on the concentration of OH − , further affecting the formation of HE-OH. It’s worth noting that the precipitation sequence of the added metal ions has a significant impact on the formation of HE-OH during the coordinating etchant process. The K sp is typically utilized to characterize the precipitation sequence of metal ions to metal hydroxides, the smaller the value of K sp , the more metal ions can be preferentially precipitated readily in the form of metal hydroxides. 34 As depicted in Fig. 1 b, the considerable variation in the pK sp (p K sp = -lg K sp ) values indicates that the precipitation sequence requisite for these ions to hydroxides varies markedly, with Cr 3+ (30.2) > Sn 2+ (27.26) > La 3+ (18.7) > Zn 2+ (16.5) > Fe 2+ (16.31) > Ni 2+ (15.26) > Co 2+ (14.23) > Cd 2+ (14.14). This suggests that Cr 3+ has the highest precipitation priority. Indeed, the conventional co-precipitation approach faces significant difficulties in the formation of high-entropy hydroxides composed of eight metal elements. This is mainly due to the considerable difference in the precipitation sequence of metal ions. To verify the controllability of the coordinating etchant method, the traditional precipitation method of a pure metal ion reaction with NaOH was carried out as a comparison test, and the products were denoted as NiCoFeCdCrLaSnZnOH NaOH . X-ray diffraction (XRD) results indicate that the eight-element hydroxide fabricated by the traditional method is not a single phase, instead, a phase separation occurs ( Supplementary Fig. 1 ). In this system, as a consequence of the precise regulation of the coordinating etchant strategy, which encompasses the concentration of metal ions, soft acid, and soft base, the co-precipitation of eight metal ions into HE-OH is achieved. Furthermore, an excessive difference in ion radius is prone to cause phase segregation. The coordinating etchant strategy presented herein also exhibits extensive applicability in the formation of HE-OH across a broad range of metal ionic radii, even for the minimum Cr 3+ (0.69 Å) and the maximum La 3+ (1.06 Å). Ultimately, the HEOs are synthesized through a thermal treatment process at 873 K in air for HE-OH. Consequently, the template-assisted route inspired by the coordinating etching strategy enables the synthesis of a diverse library of HEOs. As illustrated in Fig. 1 c, a series of spinel oxides, including ternary NiCoFe-O, quaternary NiCoFeCd-O, quaternary NiCoFeCr-O, as well as HEOs systems such as quinary NiCoFeCdCr-O, senary NiCoFeCdCrLa-O, septenary NiCoFeCdCrLaSn-O, and octonary NiCoFeCdCrLaSnZn-O have been successfully synthesized. In addition, the potential benefits of the synthesized HEOs for In addition, the potential benefits of the synthesized HEOs for catalytic applications can be elucidated through density functional theory (DFT) calculations. As illustrated by the density of states (DOS) in Fig. 1 d, the quinary high-entropy oxide exhibits a more continuous electronic structure compared to ternary (Fig. 1 e) and quaternary materials ( Supplementary Fig. 2–7 ), which facilitates the formation of highly active sites and broadens the range of adsorption energies, thereby enhancing its catalytic properties. 35 , 36 , 37 In addition, the significant overlap observed among the orbitals of all elements indicates strong bonding, which not only facilitates electron transfer between various metal sites but also provides multiple active sites for reactions. 38 In accordance with the d-band theory, the adsorption energy of reaction intermediates can be optimized by modifying the d-band center of metal sites, which can be influenced by the interaction with other metal dopants. 38 , 39 Simultaneously, the centers of the Ni-3d and Co-3d orbitals exhibited a negative shift, while the Fe-3d orbitals displayed a positive change upon the introduction of Cd and Cr ( Supplementary Fig. 8 ). Therefore, the Cd and Cr dopant plays a crucial role in modulating the electronic structure of Ni, Co, and Fe, thus leading to an optimal d-band center of Ni, Co, and Fe in NiCoFeCdCr-O for the favorable adsorption of intermediates. As illustrated in Fig. 1 f, the formation of the quinary HEOs results in a more optimal d-band center for NiCoFeCdCr-O at -2.372 eV. In comparison to NiCoFe-O (-1.325 eV), NiCoFeCd-O (-2.791 eV), and NiCoFeCr-O (-1.333 eV), this configuration of NiCoFeCdCr-O exhibits moderate binding strength with reaction intermediates, thereby facilitating product release from the surface and enhancing catalytic activity. Composition and structure of NiCoFeCdCr-O. The scanning electron microscopy (SEM) and XRD results presented in Supplementary Fig. 9a and 9b indicate that Cu 2 O exhibits a nanocube morphology, with the XRD diffraction peaks accurately corresponding to the cuprite phase of Cu 2 O (JCPDS Card Number 05-0667). The transmission electron microscopy (TEM) images further reveal a solid nanocube structure with an average size of approximately 300 nm ( Supplementary Fig. 10 ). As shown in Supplementary Fig. 11a , NiCoFeCdCr-OH exhibits a morphology of hollow nanocube, and the XRD results indicate that the diffraction peaks can be accurately assigned to classical hydroxides ( Supplementary Fig. 11b ). 34 Additionally, the TEM images and elemental distribution of NiCoFeCdCr-OH are presented in Supplementary Fig. 12 , demonstrating that the five metal elements and oxygen are uniformly and randomly distributed throughout the framework, while the interior is observed to be hollow. The XRD and TEM patterns primarily indicate that the single-phase NiCoFeCdCr-OH precursor was successfully synthesized using the coordinating etchant method. To further elucidate the coordinating etchant process in detail, a 2-minute reaction was conducted, the product was denoted NiCoFeCdCr-O 2min , and the TEM images and element distribution as shown in Supplementary Fig. 13 . The Cu element occupied the core of the nanocube reveals that the Cu 2 O is not completely coordinated etching and predominantly remains after 2 min reaction time. The Ni/Co/Fe/Cd/Cr elements are mainly distributed edges around the cube in the form of a shell composed of small nanosheets, indicating the few NiCoFeCdCr-OH derivatives are still formed even 2 min reaction between Cu 2 O and Na 2 S 2 O 3 . This observation further corroborates the efficacy of the coordinating etchant process. To further investigate the effects of the thermal treatment process on the products, various temperatures were analyzed. As illustrated in Supplementary Fig. 14 , with a gradual increase in synthesis temperature from 300 to 700°C, the hydroxide precursor undergoes thermal decomposition and subsequently transforms into a single-phase spinel structure at elevated temperatures, driven by entropy. 40 Figure 2 a and Supplementary Fig. 15a present the TEM images of NiCoFeCdCr-O, illustrating the morphology of the hollow nanocube. The nanosheets surrounding the surface of the hollow nanocube exhibit a degree of shrinkage after the annealing treatment compared to NiCoFeCdCr-OH. Furthermore, corresponding to Fig. 2 b, the atomic strain distribution pattern derived from geometric phase analysis (GPA) indicates an uneven strain distribution (Fig. 2 c), featuring numerous discontinuous yellow compressive strain regions and blue tensile strain regions. This phenomenon is linked to the incorporation of metal elements with differing ionic radii, suggesting that lattice distortion occurred in NiCoFeCdCr-O. 41 , 42 , 43 , 44 The element mapping presented in Fig. 2 d illustrates the homogeneous distribution of Ni, Co, Fe, Cd, Cr, and O elements within the quinary HEOs. Furthermore, the results obtained from inductively coupled plasma-optical emission spectrometry (ICP-OES) in Supplementary Table 1 , indicate that the metal content of the five elements is approximately uniform, thereby reinforcing the notion of a consistent elemental distribution within the high-entropy phase. Additionally, the magnified TEM images depicted in Supplementary Fig. 15b and Fig. 2 e reveal that NiCoFeCdCr-O is composed of various nanosheets oriented differently and interconnected by grain boundaries. The illustrated model of grain boundaries is presented in Fig. 2 f. 45 , 46 As illustrated in Supplementary Fig. 16 , the XRD pattern of NiCoFeCdCr-O demonstrates the establishment of a spinel structure in HEOs without any evidence of phase segregation. 47 , 48 Furthermore, the HRTEM results in Fig. 2 g and Supplementary Fig. 17 confirm the clear spacing lattice fringes of NiCoFeCdCr-O. Notably, the spacing lattice fringes of 0.245, 0.238, and 0.296 nm correspond to the typical (222) and (220) plane of spinel structure (Fd-3m) CoFe 2 O 4 (PDF#22-1086). Apart from this, elemental mapping images of ternary NiCoFe-O, quaternary NiCoFeCd-O, and NiCoFeCr-O displayed a uniform distribution of elements in Supplementary Fig. 18–20 . Besides, the XRD patterns exhibit similar information to quinary NiCoFeCdCr-O ( Supplementary Fig. 21 ). The TEM images were provided to demonstrate that the spacing lattice fringes align with the typical planes of the spinel structure CoFe 2 O 4 (PDF#22-1086) in Supplementary Fig. 22–24 , suggesting the synthesis strategy is also suitable for low-component spinel oxides. From the above results, it can be concluded that different components of oxides were synthesized by this method, and the spinel structure was retained even with the different incorporation elements. Library synthesis for HEOs. Our method for synthesizing HEOs exhibits universal applicability and can be employed to produce senary NiCoFeCdCrLa-O (Fig. 3 a), septenary NiCoFeCdCrLaSn-O (Fig. 3 b), and octonary NiCoFeCdCrLaSnZn-O (Fig. 3 c) with a hollow nanocube structure. Furthermore, the TEM results presented in Fig. 3 a-c and Supplementary Fig. 25-S27 indicate that the lattice fringe spacings correspond to the characteristic planes of the spinel structure (Fd-3m) CoFe 2 O 4 (PDF#22-1086). In Fig. 3 d, XRD patterns of all samples also reveal similar major diffraction peaks associated with the spinel phase structure (Fd-3m) without any phase separation, which aligns with the TEM findings. As illustrated in Supplementary Fig. 28 , the XRD pattern of octonary NiCoFeCdCrLaSnZn-OH undergoes a transition to that of octonary NiCoFeCdCrLaSnZn-O at varying annealing temperatures, thereby further corroborating that this strategy offers a universal and rapid synthesis method for a wide range of HEOs. The electronic structure of HEO. X-ray photoelectron spectroscopy (XPS) was utilized to analyze the surface chemical compositions and valence states of the elements. As shown in Supplementary Fig. 29 , the XPS survey spectrum confirms the successful synthesis of ternary NiCoFe-O, quaternary NiCoFeCd-O, quaternary NiCoFeCr-O, and quinary NiCoFeCdCr-O. In Supplementary Fig. 30 , it is evident that the electronic structures of Ni and O are influenced by the incorporation of Cr in both quaternary NiCoFeCr-O and NiCoFeCdCr-O when compared to ternary NiCoFe-O and quaternary NiCoFeCd-O.The emergence of a peak at O1 position from the O 1s XPS spectrum is attributed to strong interactions between Cr and O, this Cr–O interaction may also affect the electronic structure of Ni. 49 , 50 Analysis of the Cr 2p, Co 2p, Fe 2p, and Cd 3d XPS spectra presented in Supplementary Fig. 31 and S32 indicate that Cr exists as Cr 3+ , while Co, Fe, and Cd are present as Co 2+ , Fe 3+ , and Cd 2+ in NiCoFeCdCr-O respectively. Moreover, the high-resolution XPS spectra for ternary NiCoFe-O, quaternary NiCoFeCd-O, and NiCoFeCr-O demonstrate consistent valence states among these metal elements ( Supplementary Fig. 33 ), comparable to those observed in quinary NiCoFeCdCr-O, thereby indicating a similar structural configuration across samples synthesized via this strategy. The electronic structure of the catalysts was further elucidated by X-ray Absorption Fine Structure (XAFS) analysis. Analysis of the X-ray absorption near-edge structure (XANES) presented in Fig. 4 a, c, e, and i reveal that the adsorption edges of Ni, Co, Fe, and Cr K-edges in ternary NiCoFe-O, quaternary NiCoFeCd-O, quaternary NiCoFeCr-O, and quinary NiCoFeCdCr-O closely resemble those of NiO, Co 3 O 4 , α-Fe 2 O 3 and Cr 2 O 3 . This observation indicates that their oxidation states are analogous to those of the corresponding spinel oxides. Furthermore, the Cd K-edge XANES spectra elucidated the similar electron structure of Cd in quaternary NiCoFeCd-O and quinary NiCoFeCdCr-O. To further investigate the alterations in coordination configuration, an extended X-ray absorption fine structure (EXAFS) analysis was conducted. As illustrated in the Ni EXAFS spectra (Fig. 4 b), the first shell EXAFS peak at 1.63 Å corresponds to Ni-O scattering, while peaks at 2.55 Å associated with Ni-M pathways. Notably, shorter Ni-O and Ni-M bond distances were recorded for samples incorporating other metals, indicating that metal incorporation induces changes in both Ni-O and Ni-M lengths. 51 The first shell EXAFS peak observed at approximately 1.44 Å is attributed to Co-O scattering (Fig. 4 d). Peaks corresponding to Co-M1 and Co-M2 pathways were detected at 2.42 and 2.98 Å, respectively. It is noteworthy that longer Co-O and Co-M bond distances were recorded for samples incorporating other metals, indicating that such metal incorporation leads to an increase in both Co-O and Co-M lengths. 52 As illustrated in Fig. 4 f, the first coordination shell EXAFS peak at 1.47 Å corresponds to Fe-O scattering, while peaks at 2.52 Å associated with Fe-M pathways were also identified. 53 The shorter Fe-O bond and longer Fe-M bond are observed for samples incorporating other metals. 54 , 55 In Fig. 4 h, NiCoFeCd-O exhibits Cd-O and Cd-M peak positions at 1.72 and 3.01 Å, respectively. However, the Cr incorporation causes a dramatic decrease in Cd-O length and an increase in Cd-M. The Cr-O coordination is observed in Fig. 4 j, suggesting the strong effect of Cr-O. Besides, contrasting with the M-O length, major changes in Ni-M, Co-M, Fe-M, Cd-M, and Cr-M bond lengths are observed in ternary NiCoFe-O, quaternary NiCoFeCd-O, quaternary NiCoFeCr-O, and quinary NiCoFeCdCr-O. Metal incorporation significantly alters the bond length of metal-metal and diminishes the intensity of the Cd/Cr-metal peaks. Importantly, similar results are further corroborated by the EXAFS analysis of NiCoFe-O, NiCoFeCd-O, NiCoFeCr-O, NiCoFeCdCrLa-O, NiCoFeCdCrLaSn-O, and NiCoFeCdCrLaSnZn-O ( Supplementary Fig. 34–41 ). Overall, the aforementioned characterization results suggest that the high-entropy system exhibits lattice distortion upon the incorporation of various elemental atoms, which modifies interatomic coordination and electronic structure, potentially resulting in exceptional catalytic activity. Bader charge analysis further offers insight into the varying numbers of transferred electrons at the active site for ternary NiCoFe-O, quaternary NiCoFeCd-O, quaternary NiCoFeCr-O, and quinary NiCoFeCdCr-O. It indicates that oxygen tends to accept electrons, whereas Fe and Cr are more prone to electron loss, with Cd exhibiting the least tendency to lose electrons. In comparison to NiCoFe-O, the number of electrons received by oxygen in NiCoFeCdCr-O appears to have decreased, suggesting that electron transfer may have occurred among different elements (Fig. 4 k). Performance of Catalytic Hydrogenation for p-Nitrophenol. As a proof of demonstration, the catalytic performance for quinary NiCoFeCdCr-O was explored as a catalyst for the catalytic hydrogenation of p-nitrophenol (4-NP). As illustrated in Supplementary Fig. 42a , the aqueous solution of 4-NP exhibits an absorption peak at approximately 317 nm. 56 The introduction of sodium borohydride leads to the appearance of a new absorption peak around 400 nm. Following the addition of the catalyst to the solution, a decrease in the absorbance of 4-NP is observed, accompanied by the emergence of a distinct peak near 310 nm, which corresponds to 4-aminophenol (4-AP). Figure 5 a illustrates the typical absorbance changes of 4-NP during the reactions conducted at 25°C. The NiCoFeCdCr-O catalyst achieves a remarkable 100% conversion efficiency of 4-NP within 150 seconds, which is superior to ternary NiCoFe-O, quaternary NiCoFeCd-O, and quaternary NiCoFeCr-O in Supplementary Fig. 42b-d . Furthermore, a linear relationship is established in Fig. 5 b by fitting the values of ln(C t /C 0 ) against the corresponding reaction time, which aligns with first-order kinetic behavior. Consequently, the calculated apparent rate constant ( k ) for NiCoFeCdCr-O was 1.79 min − 1 (Fig. 5 c), which is 7.40, 2.82, and 1.79 times that of NiCoFe-O (0.242 min − 1 ), NiCoFeCd-O (0.635 min − 1 ) and NiCoFeCr-O (1.00 min − 1 ), respectively. Moreover, NiCoFeCdCr-O exhibited a high specific constant ( K ) of 1.53×10 6 min − 1 g − 1 . As illustrated in Fig. 5 d, Supplementary Table 2 , and Supplementary Table 3 , NiCoFeCdCr-O outperforms most reported noble metal-based catalysts and high-entropy materials for the direct hydrogenation of 4-NP. Furthermore, a linear relationship can be derived by fitting the value of ln(C t /C 0 ) under the various reaction temperatures in Fig. 5 e. The values of the k demonstrated an increase with elevated reaction temperatures, this observation can be explained by collision theory. As the system temperature rises, the intense motion of catalyst and 4-NP increases the likelihood of collisions, resulting in faster reaction rates. The final activation energy for NiCoFeCdCr-O was calculated to be 49.7 kJ/mol from the calculated k at different reaction temperatures using the Arrhenius equation. The lower the activation energy indicates the less energy required for the reaction, which is more conducive to the reaction. 57 , 58 Additionally, the performance of various 4-NP concentrations was evaluated to assess the catalytic suitability of the catalyst ( Supplementary Fig. 43 ). Reusability is widely recognized as a critical parameter for catalysts. As illustrated in Fig. 5 f, the NiCoFeCdCr-O catalyst exhibited sustained high activity over 10 cycles, with the conversion rate consistently maintained above 95%. These findings indicate that the NiCoFeCdCr-O catalyst not only demonstrates high catalytic activity but also exhibits excellent recyclability. To further explore the general applicability of the NiCoFeCdCr-O catalyst in the reduction of nitrophenolic pollutants to aminophenol, a range of nitrophenol with diverse structures was selected as probe molecules, including 2-nitrophenol (2-NP) and 3-nitrophenol (3-NP). As illustrated in Supplementary Fig. 44 , a series of successive UV–vis spectra clearly demonstrates that the NiCoFeCdCr-O catalyst facilitates the reduction of nitrophenol to their corresponding aminophenol products in the presence of NaBH 4 . In order to illustrate the superiority of the coordinating etching and precipitating method, NiCoFeCdCrO NaOH was synthesized with NaOH solution instead of Na 2 S 2 O 3 solution, and other synthesis and testing conditions remained unchanged. As shown in Supplementary Fig. 45a , the catalytic activity of NiCoFeCdCrO NaOH exhibits a precipitous decline with 4-NP being entirely degraded for more than 40 minutes. The XRD results of NiCoFeCdCrO NaOH revealed the presence of the CuO phase, indicating that Cu₂O is not completely consumed and converted into CuO following thermal treatment ( Supplementary Fig. 45b ). The findings indicate that CuO demonstrated inert catalytic activity. To verify this hypothesis, the pure CuO was obtained by direct thermal treatment of pure Cu 2 O. The performance test of pure CuO demonstrated that the catalytic activity was inferior to that of NiCoFeCdCrO NaOH ( Supplementary Fig. 45c ). Additionally, the XRD patterns indicated the formation of a pure CuO phase with high crystallinity ( Supplementary Fig. 45d ), therefore, which was consistent with the aforementioned hypothesis. In essence, the coordinating etchant method ensures the overwhelming consumption of Cu 2 O and circumvents large residues of CuO, thereby conferring upon the hollow nanocube NiCoFeCdCr-O a dominant role in the catalytic process. Conclusion In summary, we have established a library of multicomponent hollow nanocube high-entropy spinel oxides, spanning ternary to octonary compositions, synthesized through the template-assisted route inspired by coordinating etching. Our detailed investigations into the underlying synthetic mechanisms elucidate that the formation of high-entropy spinel oxides transpires via four pivotal steps: (1) The preparation of the nanocube Cu 2 O temple, (2) the liberation of hydroxide ions (OH − ) through coordinating etching reactions between soft bases and soft acids; (3) The co-precipitation of various metal cations onto the nanocube shell, leading to the formation of high-entropy metal hydroxide (HE-OH); and (4) subsequent thermal treatment of HE-OH. Experimental results indicate that the formation and stabilization of HEO nanocubes are critically dependent on the generation of HE-OH, which is achieved by meticulously controlling the balance between the precipitation rate of metal hydroxides and the synchronous coordinating etching rate towards the soft acid. Furthermore, the DFT simulation reveals a more continuous DOS near the Fermi level and a more moderate d-band center for the representative quinary NiCoFeCdCr-O hollow nanocube. Consequently, in the catalytic hydrogenation of 4-NP, this quinary NiCoFeCdCr-O demonstrates exceptional catalytic activity and cyclic stability. The proposed synthesis methodology establishes a comprehensive platform for the advancement of HEOs. Methods Reagents. Cupric sulfate pentahydrate (CuSO 4 , 99%), sodium hydroxide (NaOH, 98%), L(+)-Ascorbic acid (99.7%), ethanol absolute (CH 3 CH 2 OH), nickel chloride hexahydrate (NiCl 2 ·6H 2 O, 98%), cobalt chloride hexahydrate (CoCl 2 ·6H 2 O, 99%), ferrous sulfate (FeSO 4 ·7H 2 O, 99%), cadmium chloride hemi(pentahydrate) (CdCl 2 ·2.5H 2 O, 99%), chromic nitrate nonahydrate (Cr(NO 3 ) 3 ·9H 2 O, 99%), lanthanum nitrate hydrate (La(NO 3 ) 3 ·nH 2 O), stannous chloride dihydrate (SnCl 2 ·2H 2 O, 98%), zinc chloride (ZnSO 4 ·7H 2 O, 98%), polyvinylpyrrolidone K-30 (PVP K-30, 99%), sodium thiosulfate (NaS 2 O 3 ·5H 2 O, 99%), p-nitrophenol (4-NP, analytical grade,), 3-nitrophenol (3-NP, 99%), 2-nitrophenol (2-NP, 99%), sodium borohydride (NaBH 4 , 98%) and sodium citrate were used without any further purification. Synthesis of HEOs. The dried HE-OH was annealed in a tube oven at 600℃ for 2 h. Additionally, the NiCoFeCd-O, NiCoFeCr-O, and NiCoFe-O were synthesized by the same synthetic route without adding Cr or Cd. The NiCoFeCdCrLa-O, NiCoFeCdCrLaSn-O, and NiCoFeCdCrLaSnZn-O were synthesized by the same synthetic route with the addition of La(NO 3 ) 3 ·nH 2 O (4.9 mg), SnCl 2 ·2H 2 O (3.4 mg), and ZnSO 4 ·7H 2 O (4.3 mg). The NiCoFeCdCrO NaOH were synthesized by the same synthetic route with Na 2 S 2 O 3 replaced by NaOH. Catalytic reduction of p-nitrophenol. Typically, NaBH 4 (0.1898 g) was dissolved into 20 mL ultrapure water, and then NaBH 4 aqueous solution was added into the 20 mL of 2 mM 4-NP to make the concentration of 4-NP to be 1 mM in the catalytic system. Then, after stirring for 5 min, 20 µL of catalyst suspension (2 mg/mL) was injected quickly into the system of 4-NP and NaBH 4 to cause the hydrogenation reaction. Subsequently, 0.5 ml solution from the system was diluted to 10 ml during the reaction process at regular intervals (30 s) and then monitored through a UV–vis spectrometer. The catalyst was separated by the filtration device and dried after the reduction reaction had finished, and then the performance test was carried out again with other experimental conditions that remained unchanged for recyclability experiments with ten successive runs. ln(C t /C 0 ) = ln(A t /A 0 ) = - k t, Where k is the apparent rate constant, t is the reaction time, C t (A t ) and C 0 (A 0 ) are defined as the concentrations (absorbances) of 4-NP at time t and t = 0, respectively. K = k /m metal , where K is the ratio rate constant, m metal is the weight of the metal in the used catalyst. Conversion = (C 0 -C t )/C 0 *100%, where C 0 is the initial absorption and C t is the final absorption at a desired interval of time, t. The activation energy for the reduction of p-nitrophenol could be calculated according to the Arrhenius equation: ln k = -E a /RT + lnA, where R is the ideal gas constant (equals to 8.314 J mol − 1 K − 1 ), A is the index factor, and the slope of the logarithmic plot of rate constant ( k ) and T − 1 can be indicated as -E a /R. Declarations Data availability The data supporting the findings of this study are available within the article and its Supplementary Information files. All other relevant source data are available from the corresponding authors upon reasonable request. Acknowledgments This work was supported by National Natural Science Founda-tion of China (Grants No. U22A20143, 22201262, 22375019), Beijing Institute of Technology Research Fund Program for Young Scholars (2022CX01011). The authors thank the Center for Advanced Analysis and Gene Sequencing of Zhengzhou University and the BL14W1 in the Shanghai Synchrotron Radiation Facility for help with characterizations. Author Contributions H.S. and W.C. conceived the idea, designed the study and wrote the paper. N.Z, Y.L. performed the sample synthesis, performed most of the reactions, collected and analyzed the data, and wrote the paper. W.C. and Z.S. carried out the X-ray absorption fine structure characterizations and data analysis. Y.L., L.Z and X.W. conducted the performance measurements. H.S. Z.Z., Y.Z., X.X. and B.Z. helped to check and revise the paper. Competing interests The authors declare no competing interests. Additional information Supplementary information is available for this paper Correspondence and requests for materials should be addressed to H.S or N.Z or W.C. References Sarkar A , et al. High entropy oxides for reversible energy storage. Nat. Commun. 9 , 3400 (2018). Ding Q , et al. Tuning element distribution, structure and properties by composition in high-entropy alloys. Nature 574 , 223-227 (2019). Han L , et al. Multifunctional high-entropy materials. Nat. Rev. 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Also discoverable on Platform About Our Team In Review Editorial Policies Advisory Board Help Center Resources Author Services Accessibility API Access RSS feed Manage Cookie Preferences © Research Square 2026 | ISSN 2693-5015 (online) Privacy Policy Terms of Service Do Not Sell My Personal Information {\"props\":{\"pageProps\":{\"initialData\":{\"identity\":\"rs-6092386\",\"acceptedTermsAndConditions\":true,\"allowDirectSubmit\":false,\"archivedVersions\":[],\"articleType\":\"Article\",\"associatedPublications\":[],\"authors\":[{\"id\":422509586,\"identity\":\"18df4869-85c0-48dc-8d28-801f9de2cf86\",\"order_by\":0,\"name\":\"Huishan 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1\",\"display\":\"\",\"copyAsset\":false,\"role\":\"figure\",\"size\":367303,\"visible\":true,\"origin\":\"\",\"legend\":\"\\u003cp\\u003e\\u003cstrong\\u003eSynthesis route and theory prediction. \\u003c/strong\\u003e(\\u003cstrong\\u003ea\\u003c/strong\\u003e) Schematic illustration of the fabrication of HEOs hollow nanocube. (\\u003cstrong\\u003eb\\u003c/strong\\u003e) The\\u003cem\\u003e pK\\u003c/em\\u003e\\u003csub\\u003e\\u003cem\\u003esp\\u003c/em\\u003e\\u003c/sub\\u003e and ionic radius of different metal ions. (\\u003cstrong\\u003ec\\u003c/strong\\u003e)\\u003cstrong\\u003e \\u003c/strong\\u003eA periodic table of elements highlighting those that can form hollow nanocube HEOs in this study.\\u003cstrong\\u003e \\u003c/strong\\u003e(\\u003cstrong\\u003ed, e\\u003c/strong\\u003e) Total and partial density of states for NiCoFeCdCr-O and NiCoFe-O. (\\u003cstrong\\u003ef\\u003c/strong\\u003e) The statistics of d-band centers of NiCoFeCdCr-O, NiCoFeCr-O, NiCoFeCd-O, and NiCoFe-O.\\u003c/p\\u003e\",\"description\":\"\",\"filename\":\"1.png\",\"url\":\"https://assets-eu.researchsquare.com/files/rs-6092386/v1/415dc6f21b0c81f5c3c77322.png\"},{\"id\":77672528,\"identity\":\"aace9390-e8b1-4fea-a2be-c1bfb1008dfc\",\"added_by\":\"auto\",\"created_at\":\"2025-03-04 07:20:50\",\"extension\":\"png\",\"order_by\":2,\"title\":\"Figure 2\",\"display\":\"\",\"copyAsset\":false,\"role\":\"figure\",\"size\":688045,\"visible\":true,\"origin\":\"\",\"legend\":\"\\u003cp\\u003e\\u003cstrong\\u003eMorphology and structure of hollow nanocube NiCoFeCdCr-O. \\u003c/strong\\u003e(\\u003cstrong\\u003ea\\u003c/strong\\u003e) TEM image. (\\u003cstrong\\u003eb\\u003c/strong\\u003e) The high-resolution transmission electron microscopy (HRTEM) image. (\\u003cstrong\\u003ec\\u003c/strong\\u003e) The related atomic strain distribution originated from (\\u003cstrong\\u003eb\\u003c/strong\\u003e). (\\u003cstrong\\u003ed\\u003c/strong\\u003e) Element mapping images. (\\u003cstrong\\u003ee\\u003c/strong\\u003e) HRTEM image with abundant grain boundaries (GB) marked with white dashed lines. (\\u003cstrong\\u003ef\\u003c/strong\\u003e)\\u003cstrong\\u003e \\u003c/strong\\u003eThe model of NiCoFeCdCr-O hollow nanocube with GB. (\\u003cstrong\\u003eg\\u003c/strong\\u003e) Integrated pixel intensities of the HEO phase taken from d\\u003csub\\u003e1\\u003c/sub\\u003e and d\\u003csub\\u003e2\\u003c/sub\\u003e in (\\u003cstrong\\u003ee\\u003c/strong\\u003e).\\u003c/p\\u003e\",\"description\":\"\",\"filename\":\"2.png\",\"url\":\"https://assets-eu.researchsquare.com/files/rs-6092386/v1/3e3057859d48c1b2f5cb2b33.png\"},{\"id\":77673634,\"identity\":\"2e44fc5b-39d5-48f1-97d9-cdd4d1fd5a49\",\"added_by\":\"auto\",\"created_at\":\"2025-03-04 07:36:50\",\"extension\":\"png\",\"order_by\":3,\"title\":\"Figure 3\",\"display\":\"\",\"copyAsset\":false,\"role\":\"figure\",\"size\":561100,\"visible\":true,\"origin\":\"\",\"legend\":\"\\u003cp\\u003e\\u003cstrong\\u003eMorphology and composition of HEOs. \\u003c/strong\\u003eElement mapping and HRTEM images of (\\u003cstrong\\u003ea\\u003c/strong\\u003e) NiCoFeCdCrLa-O, (\\u003cstrong\\u003eb\\u003c/strong\\u003e) NiCoFeCdCrLaSn-O, (\\u003cstrong\\u003ec\\u003c/strong\\u003e) NiCoFeCdCrLaSnZn-O (scale bar: 200 nm). (\\u003cstrong\\u003ed\\u003c/strong\\u003e) XRD patterns of the obtained senary, septenary, and octonary HEOs.\\u003c/p\\u003e\",\"description\":\"\",\"filename\":\"3.png\",\"url\":\"https://assets-eu.researchsquare.com/files/rs-6092386/v1/0feb2bc3806a71f934eaed4b.png\"},{\"id\":77673635,\"identity\":\"c83b4b41-7f60-44f2-97b1-833ad6869242\",\"added_by\":\"auto\",\"created_at\":\"2025-03-04 07:36:50\",\"extension\":\"png\",\"order_by\":4,\"title\":\"Figure 4\",\"display\":\"\",\"copyAsset\":false,\"role\":\"figure\",\"size\":207721,\"visible\":true,\"origin\":\"\",\"legend\":\"\\u003cp\\u003e\\u003cstrong\\u003eElectron structure of HEO. \\u003c/strong\\u003e(\\u003cstrong\\u003ea\\u003c/strong\\u003e) Ni K-edge XANES spectra and corresponding (\\u003cstrong\\u003eb\\u003c/strong\\u003e) EXAFS spectra for NiCoFe-O, NiCoFeCd-O, NiCoFeCr-O, and NiCoFeCdCr-O with NiO as references. (\\u003cstrong\\u003ec\\u003c/strong\\u003e) Co K-edge XANES spectra and corresponding (\\u003cstrong\\u003ed\\u003c/strong\\u003e) EXAFS spectra for NiCoFe-O, NiCoFeCd-O, NiCoFeCdCr-O, and NiCoFeCr-O with Co\\u003csub\\u003e3\\u003c/sub\\u003eO\\u003csub\\u003e4\\u003c/sub\\u003e as references. (\\u003cstrong\\u003ee\\u003c/strong\\u003e) Fe K-edge XANES spectra and corresponding (\\u003cstrong\\u003ef\\u003c/strong\\u003e)\\u003cstrong\\u003e \\u003c/strong\\u003eEXAFS spectra for NiCoFe-O, NiCoFeCd-O, NiCoFeCr-O, and NiCoFeCdCr-O with α-Fe\\u003csub\\u003e2\\u003c/sub\\u003eO\\u003csub\\u003e3\\u003c/sub\\u003e. (\\u003cstrong\\u003eg\\u003c/strong\\u003e) Cd K-edge XANES spectra, and corresponding (\\u003cstrong\\u003eh\\u003c/strong\\u003e)\\u003cstrong\\u003e \\u003c/strong\\u003eEXAFS spectra for NiCoFeCd-O and NiCoFeCdCr-O. (\\u003cstrong\\u003ei\\u003c/strong\\u003e) Cr K-edge XANES spectra and corresponding (\\u003cstrong\\u003ej\\u003c/strong\\u003e) EXAFS spectra for NiCoFeCr-O and NiCoFeCdCr-O with Cr\\u003csub\\u003e2\\u003c/sub\\u003eO\\u003csub\\u003e3\\u003c/sub\\u003e as references. (\\u003cstrong\\u003ek\\u003c/strong\\u003e)\\u003cstrong\\u003e \\u003c/strong\\u003eBader charge of different metal atoms including O, Cd, Cr, Fe, Co, and Ni among NiCoFe-O, NiCoFeCd-O, NiCoFeCr-O, and NiCoFeCdCr-O.\\u003c/p\\u003e\",\"description\":\"\",\"filename\":\"4.png\",\"url\":\"https://assets-eu.researchsquare.com/files/rs-6092386/v1/427dc23b0f4ce098a7f84b50.png\"},{\"id\":77672530,\"identity\":\"12a54692-972d-477f-b1d9-445195b01cff\",\"added_by\":\"auto\",\"created_at\":\"2025-03-04 07:20:50\",\"extension\":\"png\",\"order_by\":5,\"title\":\"Figure 5\",\"display\":\"\",\"copyAsset\":false,\"role\":\"figure\",\"size\":164095,\"visible\":true,\"origin\":\"\",\"legend\":\"\\u003cp\\u003e\\u003cstrong\\u003eThe catalytic reduction of 4-NP to 4-AP over as-prepared catalysts. \\u003c/strong\\u003e(\\u003cstrong\\u003ea\\u003c/strong\\u003e) The UV–vis absorbance spectra of 4-NP solutions with a change of reaction time at 25℃ for NiCoFeCdCr-O. (\\u003cstrong\\u003eb\\u003c/strong\\u003e) Plots of ln(C\\u003csub\\u003et\\u003c/sub\\u003e/C\\u003csub\\u003e0\\u003c/sub\\u003e) against the reaction time of as-measured catalysts. (\\u003cstrong\\u003ec\\u003c/strong\\u003e) The corresponding histogram of rate constants. (\\u003cstrong\\u003ed\\u003c/strong\\u003e) Comparison of rate constants (\\u003cem\\u003ek\\u003c/em\\u003e) and ratio constant (\\u003cem\\u003eK\\u003c/em\\u003e) for catalytic reduction of 4-NP over NiCoFeCdCr-O with previously reported noble metal-based nanocatalysts. (\\u003cstrong\\u003ee\\u003c/strong\\u003e) Plots of ln(C\\u003csub\\u003et\\u003c/sub\\u003e/C\\u003csub\\u003e0\\u003c/sub\\u003e) against the reaction time of NiCoFeCdCr-O at different temperatures (Inset: the Arrhenius plots). (\\u003cstrong\\u003ef\\u003c/strong\\u003e) The recycling tests of NiCoFeCdCr-O for the hydrogenation of 4-NP over ten cycles.\\u003c/p\\u003e\",\"description\":\"\",\"filename\":\"5.png\",\"url\":\"https://assets-eu.researchsquare.com/files/rs-6092386/v1/029e743a3744d335e4e26c75.png\"},{\"id\":95363658,\"identity\":\"8fc92b08-86a6-4b51-80a0-b397ceee0db1\",\"added_by\":\"auto\",\"created_at\":\"2025-11-07 08:09:09\",\"extension\":\"pdf\",\"order_by\":0,\"title\":\"\",\"display\":\"\",\"copyAsset\":false,\"role\":\"manuscript-pdf\",\"size\":3173973,\"visible\":true,\"origin\":\"\",\"legend\":\"\",\"description\":\"\",\"filename\":\"manuscript.pdf\",\"url\":\"https://assets-eu.researchsquare.com/files/rs-6092386/v1/a6216b1e-c484-40f3-b929-e0061fbfc633.pdf\"},{\"id\":77672543,\"identity\":\"ae69229c-f647-43ea-a6e9-e7c0dc95b3c5\",\"added_by\":\"auto\",\"created_at\":\"2025-03-04 07:20:50\",\"extension\":\"docx\",\"order_by\":1,\"title\":\"\",\"display\":\"\",\"copyAsset\":false,\"role\":\"supplement\",\"size\":33527221,\"visible\":true,\"origin\":\"\",\"legend\":\"Supplementary Information\",\"description\":\"\",\"filename\":\"SupplementaryInformation.docx\",\"url\":\"https://assets-eu.researchsquare.com/files/rs-6092386/v1/12186d1e6e21f4bfa00b705e.docx\"}],\"financialInterests\":\"There is \\u003cb\\u003eNO\\u003c/b\\u003e Competing Interest.\",\"formattedTitle\":\"Coordinating Etching Inspired Synthesis of noble-metal-free monodisperse high-entropy oxides hollow nanocubes libraries\",\"fulltext\":[{\"header\":\"Introduction\",\"content\":\"\\u003cp\\u003eHigh-entropy oxides (HEOs) are regarded as a solid-solution phase, which can be classified into spinel, rock salt, fluorite, and perovskite structures.\\u003csup\\u003e\\u003cspan citationid=\\\"CR1\\\" class=\\\"CitationRef\\\"\\u003e1\\u003c/span\\u003e, \\u003cspan citationid=\\\"CR2\\\" class=\\\"CitationRef\\\"\\u003e2\\u003c/span\\u003e, \\u003cspan citationid=\\\"CR3\\\" class=\\\"CitationRef\\\"\\u003e3\\u003c/span\\u003e, \\u003cspan citationid=\\\"CR4\\\" class=\\\"CitationRef\\\"\\u003e4\\u003c/span\\u003e, \\u003cspan citationid=\\\"CR5\\\" class=\\\"CitationRef\\\"\\u003e5\\u003c/span\\u003e\\u003c/sup\\u003e They have emerged as a significant focus of research due to their disordered arrangement, interactions among multiple principal elements, and the promotion of entropy.\\u003csup\\u003e\\u003cspan citationid=\\\"CR6\\\" class=\\\"CitationRef\\\"\\u003e6\\u003c/span\\u003e, \\u003cspan citationid=\\\"CR7\\\" class=\\\"CitationRef\\\"\\u003e7\\u003c/span\\u003e, \\u003cspan citationid=\\\"CR8\\\" class=\\\"CitationRef\\\"\\u003e8\\u003c/span\\u003e, \\u003cspan citationid=\\\"CR9\\\" class=\\\"CitationRef\\\"\\u003e9\\u003c/span\\u003e\\u003c/sup\\u003e Moreover, the configurational entropy of high-entropy oxides significantly exceeds that of individual monometallic oxides, suggesting that high-entropy oxides exhibit greater thermodynamic stability than their monometallic counterparts at finite temperatures.\\u003csup\\u003e\\u003cspan citationid=\\\"CR10\\\" class=\\\"CitationRef\\\"\\u003e10\\u003c/span\\u003e, \\u003cspan citationid=\\\"CR11\\\" class=\\\"CitationRef\\\"\\u003e11\\u003c/span\\u003e, \\u003cspan citationid=\\\"CR12\\\" class=\\\"CitationRef\\\"\\u003e12\\u003c/span\\u003e, \\u003cspan citationid=\\\"CR13\\\" class=\\\"CitationRef\\\"\\u003e13\\u003c/span\\u003e\\u003c/sup\\u003e The previously reported synthesis methods for HEOs are characterized by prolonged heating durations, elevated temperatures, and substantial energy consumption. For instance, they involve the mixing of metal salts followed by heating to temperatures of 900\\u0026deg;C or higher to achieve sintering into a single phase.\\u003csup\\u003e\\u003cspan citationid=\\\"CR14\\\" class=\\\"CitationRef\\\"\\u003e14\\u003c/span\\u003e, \\u003cspan citationid=\\\"CR15\\\" class=\\\"CitationRef\\\"\\u003e15\\u003c/span\\u003e\\u003c/sup\\u003e However, the high temperatures associated with this process can lead to irregular molten bulk formation, limited adjustability of components, and a propensity for phase separation, which may hinder the accessibility of active sites and impair the catalytic reaction process.\\u003csup\\u003e\\u003cspan citationid=\\\"CR16\\\" class=\\\"CitationRef\\\"\\u003e16\\u003c/span\\u003e, \\u003cspan citationid=\\\"CR17\\\" class=\\\"CitationRef\\\"\\u003e17\\u003c/span\\u003e\\u003c/sup\\u003e Consequently, there is an urgent need for a novel synthesis strategy that is both rapid and controllable, aimed at minimizing heating duration and temperature while effectively managing morphological characteristics.\\u003csup\\u003e\\u003cspan citationid=\\\"CR18\\\" class=\\\"CitationRef\\\"\\u003e18\\u003c/span\\u003e, \\u003cspan citationid=\\\"CR19\\\" class=\\\"CitationRef\\\"\\u003e19\\u003c/span\\u003e\\u003c/sup\\u003e\\u003c/p\\u003e \\u003cp\\u003eThe utilization of metal hydroxides as precursors constitutes a common approach for the synthesis of metallic oxides. It has been reported that monocomponent, binary, or even ternary metal hydroxides with various components and morphologies can be fabricated through the solution method. Subsequently, the corresponding metal oxides are obtained via low-temperature heat treatment while retaining the original morphologies of the metal hydroxides.\\u003csup\\u003e\\u003cspan citationid=\\\"CR20\\\" class=\\\"CitationRef\\\"\\u003e20\\u003c/span\\u003e, \\u003cspan citationid=\\\"CR21\\\" class=\\\"CitationRef\\\"\\u003e21\\u003c/span\\u003e, \\u003cspan citationid=\\\"CR22\\\" class=\\\"CitationRef\\\"\\u003e22\\u003c/span\\u003e, \\u003cspan citationid=\\\"CR23\\\" class=\\\"CitationRef\\\"\\u003e23\\u003c/span\\u003e, \\u003cspan citationid=\\\"CR24\\\" class=\\\"CitationRef\\\"\\u003e24\\u003c/span\\u003e\\u003c/sup\\u003e Nevertheless, the incorporation of five or more metallic elements into metal hydroxide precursors poses a significant challenge due to the complex co-precipitation kinetics arising from the disparate physicochemical properties of different metal cations and standard solubility product constants (\\u003cem\\u003eK\\u003c/em\\u003e\\u003csub\\u003e\\u003cem\\u003esp\\u003c/em\\u003e\\u003c/sub\\u003e) of metal hydroxides.\\u003csup\\u003e\\u003cspan citationid=\\\"CR25\\\" class=\\\"CitationRef\\\"\\u003e25\\u003c/span\\u003e\\u003c/sup\\u003e Furthermore, in a multiple metal hydroxide precursor system, the precipitation sequence of metal species cannot be solely evaluated by \\u003cem\\u003eK\\u003c/em\\u003e\\u003csub\\u003e\\u003cem\\u003esp\\u003c/em\\u003e\\u003c/sub\\u003e. It may also be influenced by factors such as coordination environments, surface energies, organic additives, and the selection of precipitating agents. These variables complicate the control of nucleation and crystal growth processes, which can further affect the morphology of the resulting products.\\u003csup\\u003e\\u003cspan citationid=\\\"CR20\\\" class=\\\"CitationRef\\\"\\u003e20\\u003c/span\\u003e, \\u003cspan citationid=\\\"CR26\\\" class=\\\"CitationRef\\\"\\u003e26\\u003c/span\\u003e\\u003c/sup\\u003e Consequently, it is crucial to regulate the co-precipitation process and the morphology of metal hydroxide precursors to achieve the formation of single-phase high-entropy oxides.\\u003c/p\\u003e \\u003cp\\u003eMorphology is a critical property of catalysts, influencing the mass transfer rate as well as the adsorption and desorption of intermediates and products, thereby exerting a significant impact on catalytic performance.\\u003csup\\u003e\\u003cspan citationid=\\\"CR27\\\" class=\\\"CitationRef\\\"\\u003e27\\u003c/span\\u003e\\u003c/sup\\u003e Morphological engineering, particularly with respect to regulating dimensionality and size, has been demonstrated as an effective strategy for enhancing physicochemical properties and introducing novel functionalities in catalysts.\\u003csup\\u003e\\u003cspan citationid=\\\"CR28\\\" class=\\\"CitationRef\\\"\\u003e28\\u003c/span\\u003e\\u003c/sup\\u003e In particular, three-dimensional hollow architectures that expose high-density active sites and provide additional channels for ionic transport and solution diffusion can shorten the charge transfer pathway and enhance the interaction between reactants and catalysts, thereby significantly improving catalytic efficiency.\\u003csup\\u003e\\u003cspan citationid=\\\"CR29\\\" class=\\\"CitationRef\\\"\\u003e29\\u003c/span\\u003e, \\u003cspan citationid=\\\"CR30\\\" class=\\\"CitationRef\\\"\\u003e30\\u003c/span\\u003e\\u003c/sup\\u003e However, the construction of three-dimensional hollow architectures in HEOs is seldom reported.\\u003c/p\\u003e \\u003cp\\u003eIn this study, we present a novel and versatile synthetic method for fabricating hollow nanocube HEOs composed of up to eight metallic elements, by a template-assisted route inspired by coordinating etching. The essence of this distinctive strategy hinges on (1) the preparation of the Cu\\u003csub\\u003e2\\u003c/sub\\u003eO nanocube template, (2) the release of hydroxide ions (OH⁻) through coordinating etching reactions between a soft base and a soft acid, (3) the co-precipitation of high-entropy metal hydroxides (HE-OH) onto the nanocube shell, and (4) the thermal treatment of HE-OH precursors. This method is achieved by meticulously controlling the balance between the precipitation rate of metal hydroxides and the synchronous coordinating etching rate towards the soft acid. As a demonstration of the catalytic concept, the quinary NiCoFeCdCr-O exhibits a high rate constant (\\u003cem\\u003ek\\u003c/em\\u003e) of 1.79 min⁻\\u0026sup1; for the hydrogenation of p-nitrophenol. Furthermore, NiCoFeCdCr-O demonstrates exceptional stability over 10 cycles, with conversion rates maintained above 95%. Density functional theory (DFT) simulations reveal that the outstanding performance can be ascribed to a more continuous density of states (DOS) near the Fermi level and a more favorable d-band center in HEOs. Our systematic investigation provides valuable insights for the future design of multi-component catalysts with tailored morphologies.\\u003c/p\\u003e\"},{\"header\":\"Results\",\"content\":\"\\u003cp\\u003e\\u003cstrong\\u003eTheoretical orientation.\\u003c/strong\\u003e The template-assisted route inspired by the coordinating etching strategy can be utilized to synthesize metal high-entropy hydroxide precursors, achieved by carefully balancing the precipitation rate of metal hydroxides with the synchronous coordinating etching rate towards the soft acid.\\u003csup\\u003e\\u003cspan class=\\\"CitationRef\\\"\\u003e20\\u003c/span\\u003e, \\u003cspan class=\\\"CitationRef\\\"\\u003e31\\u003c/span\\u003e, \\u003cspan class=\\\"CitationRef\\\"\\u003e32\\u003c/span\\u003e, \\u003cspan class=\\\"CitationRef\\\"\\u003e33\\u003c/span\\u003e\\u003c/sup\\u003e The synthetic route is illustrated in Fig.\\u0026nbsp;\\u003cspan class=\\\"InternalRef\\\"\\u003e1\\u003c/span\\u003ea, and the general chemical process can be described as follows:\\u003c/p\\u003e\\n\\u003cp\\u003eCu\\u003csub\\u003e2\\u003c/sub\\u003eO\\u0026thinsp;+\\u0026thinsp;xS\\u003csub\\u003e2\\u003c/sub\\u003eO\\u003csub\\u003e3\\u003c/sub\\u003e\\u003csup\\u003e2-\\u003c/sup\\u003e+H\\u003csub\\u003e2\\u003c/sub\\u003eO \\u0026rarr; [Cu\\u003csub\\u003e2\\u003c/sub\\u003e(S\\u003csub\\u003e2\\u003c/sub\\u003eO\\u003csub\\u003e3\\u003c/sub\\u003e\\u003csup\\u003e2-\\u003c/sup\\u003e)\\u003csub\\u003ex\\u003c/sub\\u003e]\\u003csup\\u003e2-2x\\u003c/sup\\u003e+2OH\\u003csup\\u003e-\\u003c/sup\\u003e (1)\\u003c/p\\u003e\\n\\u003cdiv id=\\\"Sec3\\\" class=\\\"Section2\\\"\\u003e\\n \\u003cp\\u003eS\\u003csub\\u003e2\\u003c/sub\\u003eO\\u003csub\\u003e3\\u003c/sub\\u003e\\u003csup\\u003e2-\\u003c/sup\\u003e+H\\u003csub\\u003e2\\u003c/sub\\u003eO ⇌ HS\\u003csub\\u003e2\\u003c/sub\\u003eO\\u003csub\\u003e3\\u003c/sub\\u003e\\u003csup\\u003e2-\\u003c/sup\\u003e+ OH\\u003csup\\u003e-\\u003c/sup\\u003e (2)\\u003c/p\\u003e\\n \\u003cp\\u003eM\\u003csup\\u003ex+\\u003c/sup\\u003e + xOH\\u003csup\\u003e-\\u003c/sup\\u003e \\u0026rarr; M(OH)\\u003csub\\u003ex\\u003c/sub\\u003e (3)\\u003c/p\\u003e\\n \\u003cp\\u003eInitially, the nanocube Cu\\u003csub\\u003e2\\u003c/sub\\u003eO was synthesized to function as a soft acid and the soft base Na\\u003csub\\u003e2\\u003c/sub\\u003eS\\u003csub\\u003e2\\u003c/sub\\u003eO\\u003csub\\u003e3\\u003c/sub\\u003e was adopted as the coordinating etchant. In accordance with Pearson\\u0026apos;s hard and soft acid-base principle, soft Lewis acids can form stable complexes with soft bases. Consequently, the soft acid characteristic of Cu\\u003csup\\u003e+\\u003c/sup\\u003e within the Cu\\u003csub\\u003e2\\u003c/sub\\u003eO nanocubes reacts with the soft base ligand (S\\u003csub\\u003e2\\u003c/sub\\u003eO\\u003csub\\u003e3\\u003c/sub\\u003e\\u003csup\\u003e2-\\u003c/sup\\u003e) to form the soluble complex [Cu\\u003csub\\u003e2\\u003c/sub\\u003e(S\\u003csub\\u003e2\\u003c/sub\\u003eO\\u003csub\\u003e3\\u003c/sub\\u003e)\\u003csub\\u003ex\\u003c/sub\\u003e]\\u003csup\\u003e2\\u0026minus;2x\\u003c/sup\\u003e (Eq.\\u0026nbsp;1), since the soft-soft interaction of Cu\\u003csup\\u003e+\\u003c/sup\\u003e\\u0026minus;S\\u003csub\\u003e2\\u003c/sub\\u003eO\\u003csub\\u003e3\\u003c/sub\\u003e\\u003csup\\u003e2-\\u003c/sup\\u003e is significantly stronger than the soft-hard interaction of Cu\\u003csup\\u003e+\\u003c/sup\\u003e\\u0026minus;O\\u003csup\\u003e2-\\u003c/sup\\u003e within Cu\\u003csub\\u003e2\\u003c/sub\\u003eO nanocubes. Apart from the OH\\u003csup\\u003e\\u0026minus;\\u003c/sup\\u003e released during the etching of Cu\\u003csub\\u003e2\\u003c/sub\\u003eO, there are certain OH\\u003csup\\u003e\\u0026minus;\\u003c/sup\\u003e originated from the hydrolysis of S\\u003csub\\u003e2\\u003c/sub\\u003eO\\u003csub\\u003e3\\u003c/sub\\u003e\\u003csup\\u003e2\\u0026minus;\\u003c/sup\\u003e (Eq.\\u0026nbsp;2). Consequently, the other added metal ions (M\\u003csup\\u003ex+\\u003c/sup\\u003e) reacted with OH\\u003csup\\u003e\\u0026minus;\\u003c/sup\\u003e and concurrently began to precipitate (Eq.\\u0026nbsp;3). The shell structure M(OH)\\u003csub\\u003ex\\u003c/sub\\u003e (denoted as HE-OH) prefers to form around the etching interface where the local concentration of OH\\u003csup\\u003e\\u0026minus;\\u003c/sup\\u003e is maximized. The synchronous chemical reactions delineated herein guarantee that the exterior of the HE-OH shell precisely replicates the geometry of the Cu\\u003csub\\u003e2\\u003c/sub\\u003eO nanocubes.\\u003c/p\\u003e\\n \\u003cp\\u003eAn alkaline environment is crucial for the co-deposition of multi-metal ions to form metal hydroxides. In this system, the control of the quantities and ratios of Cu\\u003csub\\u003e2\\u003c/sub\\u003eO and Na\\u003csub\\u003e2\\u003c/sub\\u003eS\\u003csub\\u003e2\\u003c/sub\\u003eO\\u003csub\\u003e3\\u003c/sub\\u003e exerts a substantial impact on the concentration of OH\\u003csup\\u003e\\u0026minus;\\u003c/sup\\u003e, further affecting the formation of HE-OH. It\\u0026rsquo;s worth noting that the precipitation sequence of the added metal ions has a significant impact on the formation of HE-OH during the coordinating etchant process. The \\u003cem\\u003eK\\u003c/em\\u003e\\u003csub\\u003e\\u003cem\\u003esp\\u003c/em\\u003e\\u003c/sub\\u003e is typically utilized to characterize the precipitation sequence of metal ions to metal hydroxides, the smaller the value of \\u003cem\\u003eK\\u003c/em\\u003e\\u003csub\\u003e\\u003cem\\u003esp\\u003c/em\\u003e\\u003c/sub\\u003e, the more metal ions can be preferentially precipitated readily in the form of metal hydroxides.\\u003csup\\u003e\\u003cspan class=\\\"CitationRef\\\"\\u003e34\\u003c/span\\u003e\\u003c/sup\\u003e As depicted in Fig.\\u0026nbsp;\\u003cspan class=\\\"InternalRef\\\"\\u003e1\\u003c/span\\u003eb, the considerable variation in the \\u003cem\\u003epK\\u003c/em\\u003e\\u003csub\\u003e\\u003cem\\u003esp\\u003c/em\\u003e\\u003c/sub\\u003e (p\\u003cem\\u003eK\\u003c/em\\u003e\\u003csub\\u003e\\u003cem\\u003esp\\u003c/em\\u003e\\u003c/sub\\u003e = -lg\\u003cem\\u003eK\\u003c/em\\u003e\\u003csub\\u003e\\u003cem\\u003esp\\u003c/em\\u003e\\u003c/sub\\u003e) values indicates that the precipitation sequence requisite for these ions to hydroxides varies markedly, with Cr\\u003csup\\u003e3+\\u003c/sup\\u003e (30.2)\\u0026thinsp;\\u0026gt;\\u0026thinsp;Sn\\u003csup\\u003e2+\\u003c/sup\\u003e (27.26)\\u0026thinsp;\\u0026gt;\\u0026thinsp;La\\u003csup\\u003e3+\\u003c/sup\\u003e (18.7)\\u0026thinsp;\\u0026gt;\\u0026thinsp;Zn\\u003csup\\u003e2+\\u003c/sup\\u003e (16.5)\\u0026thinsp;\\u0026gt;\\u0026thinsp;Fe\\u003csup\\u003e2+\\u003c/sup\\u003e (16.31)\\u0026thinsp;\\u0026gt;\\u0026thinsp;Ni\\u003csup\\u003e2+\\u003c/sup\\u003e (15.26)\\u0026thinsp;\\u0026gt;\\u0026thinsp;Co\\u003csup\\u003e2+\\u003c/sup\\u003e (14.23)\\u0026thinsp;\\u0026gt;\\u0026thinsp;Cd\\u003csup\\u003e2+\\u003c/sup\\u003e (14.14). This suggests that Cr\\u003csup\\u003e3+\\u003c/sup\\u003e has the highest precipitation priority. Indeed, the conventional co-precipitation approach faces significant difficulties in the formation of high-entropy hydroxides composed of eight metal elements. This is mainly due to the considerable difference in the precipitation sequence of metal ions. To verify the controllability of the coordinating etchant method, the traditional precipitation method of a pure metal ion reaction with NaOH was carried out as a comparison test, and the products were denoted as NiCoFeCdCrLaSnZnOH\\u003csub\\u003eNaOH\\u003c/sub\\u003e. X-ray diffraction (XRD) results indicate that the eight-element hydroxide fabricated by the traditional method is not a single phase, instead, a phase separation occurs (\\u003cstrong\\u003eSupplementary Fig.\\u0026nbsp;1\\u003c/strong\\u003e). In this system, as a consequence of the precise regulation of the coordinating etchant strategy, which encompasses the concentration of metal ions, soft acid, and soft base, the co-precipitation of eight metal ions into HE-OH is achieved. Furthermore, an excessive difference in ion radius is prone to cause phase segregation. The coordinating etchant strategy presented herein also exhibits extensive applicability in the formation of HE-OH across a broad range of metal ionic radii, even for the minimum Cr\\u003csup\\u003e3+\\u003c/sup\\u003e (0.69 \\u0026Aring;) and the maximum La\\u003csup\\u003e3+\\u003c/sup\\u003e (1.06 \\u0026Aring;).\\u003c/p\\u003e\\n \\u003cp\\u003eUltimately, the HEOs are synthesized through a thermal treatment process at 873 K in air for HE-OH. Consequently, the template-assisted route inspired by the coordinating etching strategy enables the synthesis of a diverse library of HEOs. As illustrated in Fig. \\u003cspan class=\\\"InternalRef\\\"\\u003e1\\u003c/span\\u003ec, a series of spinel oxides, including ternary NiCoFe-O, quaternary NiCoFeCd-O, quaternary NiCoFeCr-O, as well as HEOs systems such as quinary NiCoFeCdCr-O, senary NiCoFeCdCrLa-O, septenary NiCoFeCdCrLaSn-O, and octonary NiCoFeCdCrLaSnZn-O have been successfully synthesized.\\u003c/p\\u003e\\n \\u003cp\\u003eIn addition, the potential benefits of the synthesized HEOs for In addition, the potential benefits of the synthesized HEOs for catalytic applications can be elucidated through density functional theory (DFT) calculations. As illustrated by the density of states (DOS) in Fig. \\u003cspan class=\\\"InternalRef\\\"\\u003e1\\u003c/span\\u003ed, the quinary high-entropy oxide exhibits a more continuous electronic structure compared to ternary (Fig. \\u003cspan class=\\\"InternalRef\\\"\\u003e1\\u003c/span\\u003ee) and quaternary materials (\\u003cstrong\\u003eSupplementary Fig.\\u0026nbsp;2\\u0026ndash;7\\u003c/strong\\u003e), which facilitates the formation of highly active sites and broadens the range of adsorption energies, thereby enhancing its catalytic properties.\\u003csup\\u003e\\u003cspan class=\\\"CitationRef\\\"\\u003e35\\u003c/span\\u003e, \\u003cspan class=\\\"CitationRef\\\"\\u003e36\\u003c/span\\u003e, \\u003cspan class=\\\"CitationRef\\\"\\u003e37\\u003c/span\\u003e\\u003c/sup\\u003e In addition, the significant overlap observed among the orbitals of all elements indicates strong bonding, which not only facilitates electron transfer between various metal sites but also provides multiple active sites for reactions.\\u003csup\\u003e\\u003cspan class=\\\"CitationRef\\\"\\u003e38\\u003c/span\\u003e\\u003c/sup\\u003e In accordance with the d-band theory, the adsorption energy of reaction intermediates can be optimized by modifying the d-band center of metal sites, which can be influenced by the interaction with other metal dopants.\\u003csup\\u003e\\u003cspan class=\\\"CitationRef\\\"\\u003e38\\u003c/span\\u003e, \\u003cspan class=\\\"CitationRef\\\"\\u003e39\\u003c/span\\u003e\\u003c/sup\\u003e Simultaneously, the centers of the Ni-3d and Co-3d orbitals exhibited a negative shift, while the Fe-3d orbitals displayed a positive change upon the introduction of Cd and Cr (\\u003cstrong\\u003eSupplementary Fig.\\u0026nbsp;8\\u003c/strong\\u003e). Therefore, the Cd and Cr dopant plays a crucial role in modulating the electronic structure of Ni, Co, and Fe, thus leading to an optimal d-band center of Ni, Co, and Fe in NiCoFeCdCr-O for the favorable adsorption of intermediates. As illustrated in Fig. \\u003cspan class=\\\"InternalRef\\\"\\u003e1\\u003c/span\\u003ef, the formation of the quinary HEOs results in a more optimal d-band center for NiCoFeCdCr-O at -2.372 eV. In comparison to NiCoFe-O (-1.325 eV), NiCoFeCd-O (-2.791 eV), and NiCoFeCr-O (-1.333 eV), this configuration of NiCoFeCdCr-O exhibits moderate binding strength with reaction intermediates, thereby facilitating product release from the surface and enhancing catalytic activity.\\u003c/p\\u003e\\n \\u003cp\\u003e\\u003cstrong\\u003eComposition and structure of NiCoFeCdCr-O.\\u003c/strong\\u003e The scanning electron microscopy (SEM) and XRD results presented in \\u003cstrong\\u003eSupplementary Fig.\\u0026nbsp;9a and 9b\\u003c/strong\\u003e indicate that Cu\\u003csub\\u003e2\\u003c/sub\\u003eO exhibits a nanocube morphology, with the XRD diffraction peaks accurately corresponding to the cuprite phase of Cu\\u003csub\\u003e2\\u003c/sub\\u003eO (JCPDS Card Number 05-0667). The transmission electron microscopy (TEM) images further reveal a solid nanocube structure with an average size of approximately 300 nm (\\u003cstrong\\u003eSupplementary Fig.\\u0026nbsp;10\\u003c/strong\\u003e). As shown in \\u003cstrong\\u003eSupplementary Fig.\\u0026nbsp;11a\\u003c/strong\\u003e, NiCoFeCdCr-OH exhibits a morphology of hollow nanocube, and the XRD results indicate that the diffraction peaks can be accurately assigned to classical hydroxides (\\u003cstrong\\u003eSupplementary Fig.\\u0026nbsp;11b\\u003c/strong\\u003e).\\u003csup\\u003e\\u003cspan class=\\\"CitationRef\\\"\\u003e34\\u003c/span\\u003e\\u003c/sup\\u003e Additionally, the TEM images and elemental distribution of NiCoFeCdCr-OH are presented in \\u003cstrong\\u003eSupplementary Fig.\\u0026nbsp;12\\u003c/strong\\u003e, demonstrating that the five metal elements and oxygen are uniformly and randomly distributed throughout the framework, while the interior is observed to be hollow. The XRD and TEM patterns primarily indicate that the single-phase NiCoFeCdCr-OH precursor was successfully synthesized using the coordinating etchant method. To further elucidate the coordinating etchant process in detail, a 2-minute reaction was conducted, the product was denoted NiCoFeCdCr-O\\u003csub\\u003e2min\\u003c/sub\\u003e, and the TEM images and element distribution as shown in \\u003cstrong\\u003eSupplementary Fig.\\u0026nbsp;13\\u003c/strong\\u003e. The Cu element occupied the core of the nanocube reveals that the Cu\\u003csub\\u003e2\\u003c/sub\\u003eO is not completely coordinated etching and predominantly remains after 2 min reaction time. The Ni/Co/Fe/Cd/Cr elements are mainly distributed edges around the cube in the form of a shell composed of small nanosheets, indicating the few NiCoFeCdCr-OH derivatives are still formed even 2 min reaction between Cu\\u003csub\\u003e2\\u003c/sub\\u003eO and Na\\u003csub\\u003e2\\u003c/sub\\u003eS\\u003csub\\u003e2\\u003c/sub\\u003eO\\u003csub\\u003e3\\u003c/sub\\u003e. This observation further corroborates the efficacy of the coordinating etchant process. To further investigate the effects of the thermal treatment process on the products, various temperatures were analyzed. As illustrated in \\u003cstrong\\u003eSupplementary Fig.\\u0026nbsp;14\\u003c/strong\\u003e, with a gradual increase in synthesis temperature from 300 to 700\\u0026deg;C, the hydroxide precursor undergoes thermal decomposition and subsequently transforms into a single-phase spinel structure at elevated temperatures, driven by entropy.\\u003csup\\u003e\\u003cspan class=\\\"CitationRef\\\"\\u003e40\\u003c/span\\u003e\\u003c/sup\\u003e\\u003c/p\\u003e\\n \\u003cp\\u003eFigure \\u003cspan class=\\\"InternalRef\\\"\\u003e2\\u003c/span\\u003ea and \\u003cstrong\\u003eSupplementary Fig.\\u0026nbsp;15a\\u003c/strong\\u003e present the TEM images of NiCoFeCdCr-O, illustrating the morphology of the hollow nanocube. The nanosheets surrounding the surface of the hollow nanocube exhibit a degree of shrinkage after the annealing treatment compared to NiCoFeCdCr-OH. Furthermore, corresponding to Fig. \\u003cspan class=\\\"InternalRef\\\"\\u003e2\\u003c/span\\u003eb, the atomic strain distribution pattern derived from geometric phase analysis (GPA) indicates an uneven strain distribution (Fig. \\u003cspan class=\\\"InternalRef\\\"\\u003e2\\u003c/span\\u003ec), featuring numerous discontinuous yellow compressive strain regions and blue tensile strain regions. This phenomenon is linked to the incorporation of metal elements with differing ionic radii, suggesting that lattice distortion occurred in NiCoFeCdCr-O.\\u003csup\\u003e\\u003cspan class=\\\"CitationRef\\\"\\u003e41\\u003c/span\\u003e, \\u003cspan class=\\\"CitationRef\\\"\\u003e42\\u003c/span\\u003e, \\u003cspan class=\\\"CitationRef\\\"\\u003e43\\u003c/span\\u003e, \\u003cspan class=\\\"CitationRef\\\"\\u003e44\\u003c/span\\u003e\\u003c/sup\\u003e The element mapping presented in Fig. \\u003cspan class=\\\"InternalRef\\\"\\u003e2\\u003c/span\\u003ed illustrates the homogeneous distribution of Ni, Co, Fe, Cd, Cr, and O elements within the quinary HEOs. Furthermore, the results obtained from inductively coupled plasma-optical emission spectrometry (ICP-OES) in \\u003cstrong\\u003eSupplementary Table\\u0026nbsp;1\\u003c/strong\\u003e, indicate that the metal content of the five elements is approximately uniform, thereby reinforcing the notion of a consistent elemental distribution within the high-entropy phase. Additionally, the magnified TEM images depicted in \\u003cstrong\\u003eSupplementary Fig.\\u0026nbsp;15b\\u003c/strong\\u003e and Fig. \\u003cspan class=\\\"InternalRef\\\"\\u003e2\\u003c/span\\u003ee reveal that NiCoFeCdCr-O is composed of various nanosheets oriented differently and interconnected by grain boundaries. The illustrated model of grain boundaries is presented in Fig. \\u003cspan class=\\\"InternalRef\\\"\\u003e2\\u003c/span\\u003ef.\\u003csup\\u003e\\u003cspan class=\\\"CitationRef\\\"\\u003e45\\u003c/span\\u003e, \\u003cspan class=\\\"CitationRef\\\"\\u003e46\\u003c/span\\u003e\\u003c/sup\\u003e As illustrated in \\u003cstrong\\u003eSupplementary Fig.\\u0026nbsp;16\\u003c/strong\\u003e, the XRD pattern of NiCoFeCdCr-O demonstrates the establishment of a spinel structure in HEOs without any evidence of phase segregation.\\u003csup\\u003e\\u003cspan class=\\\"CitationRef\\\"\\u003e47\\u003c/span\\u003e, \\u003cspan class=\\\"CitationRef\\\"\\u003e48\\u003c/span\\u003e\\u003c/sup\\u003e Furthermore, the HRTEM results in Fig. \\u003cspan class=\\\"InternalRef\\\"\\u003e2\\u003c/span\\u003eg and \\u003cstrong\\u003eSupplementary Fig.\\u0026nbsp;17\\u003c/strong\\u003e confirm the clear spacing lattice fringes of NiCoFeCdCr-O. Notably, the spacing lattice fringes of 0.245, 0.238, and 0.296 nm correspond to the typical (222) and (220) plane of spinel structure (Fd-3m) CoFe\\u003csub\\u003e2\\u003c/sub\\u003eO\\u003csub\\u003e4\\u003c/sub\\u003e (PDF#22-1086).\\u003c/p\\u003e\\n \\u003cp\\u003eApart from this, elemental mapping images of ternary NiCoFe-O, quaternary NiCoFeCd-O, and NiCoFeCr-O displayed a uniform distribution of elements in \\u003cstrong\\u003eSupplementary Fig.\\u0026nbsp;18\\u0026ndash;20\\u003c/strong\\u003e. Besides, the XRD patterns exhibit similar information to quinary NiCoFeCdCr-O (\\u003cstrong\\u003eSupplementary Fig.\\u0026nbsp;21\\u003c/strong\\u003e). The TEM images were provided to demonstrate that the spacing lattice fringes align with the typical planes of the spinel structure CoFe\\u003csub\\u003e2\\u003c/sub\\u003eO\\u003csub\\u003e4\\u003c/sub\\u003e (PDF#22-1086) in \\u003cstrong\\u003eSupplementary Fig.\\u0026nbsp;22\\u0026ndash;24\\u003c/strong\\u003e, suggesting the synthesis strategy is also suitable for low-component spinel oxides. From the above results, it can be concluded that different components of oxides were synthesized by this method, and the spinel structure was retained even with the different incorporation elements.\\u003c/p\\u003e\\n \\u003cp\\u003e\\u003cstrong\\u003eLibrary synthesis for HEOs.\\u003c/strong\\u003e Our method for synthesizing HEOs exhibits universal applicability and can be employed to produce senary NiCoFeCdCrLa-O (Fig. \\u003cspan class=\\\"InternalRef\\\"\\u003e3\\u003c/span\\u003ea), septenary NiCoFeCdCrLaSn-O (Fig. \\u003cspan class=\\\"InternalRef\\\"\\u003e3\\u003c/span\\u003eb), and octonary NiCoFeCdCrLaSnZn-O (Fig. \\u003cspan class=\\\"InternalRef\\\"\\u003e3\\u003c/span\\u003ec) with a hollow nanocube structure. Furthermore, the TEM results presented in Fig. \\u003cspan class=\\\"InternalRef\\\"\\u003e3\\u003c/span\\u003ea-c and \\u003cstrong\\u003eSupplementary Fig.\\u0026nbsp;25-S27\\u003c/strong\\u003e indicate that the lattice fringe spacings correspond to the characteristic planes of the spinel structure (Fd-3m) CoFe\\u003csub\\u003e2\\u003c/sub\\u003eO\\u003csub\\u003e4\\u003c/sub\\u003e (PDF#22-1086). In Fig. \\u003cspan class=\\\"InternalRef\\\"\\u003e3\\u003c/span\\u003ed, XRD patterns of all samples also reveal similar major diffraction peaks associated with the spinel phase structure (Fd-3m) without any phase separation, which aligns with the TEM findings. As illustrated in \\u003cstrong\\u003eSupplementary Fig.\\u0026nbsp;28\\u003c/strong\\u003e, the XRD pattern of octonary NiCoFeCdCrLaSnZn-OH undergoes a transition to that of octonary NiCoFeCdCrLaSnZn-O at varying annealing temperatures, thereby further corroborating that this strategy offers a universal and rapid synthesis method for a wide range of HEOs.\\u003c/p\\u003e\\n \\u003cp\\u003e\\u003cstrong\\u003eThe electronic structure of HEO.\\u003c/strong\\u003e X-ray photoelectron spectroscopy (XPS) was utilized to analyze the surface chemical compositions and valence states of the elements. As shown in \\u003cstrong\\u003eSupplementary Fig.\\u0026nbsp;29\\u003c/strong\\u003e, the XPS survey spectrum confirms the successful synthesis of ternary NiCoFe-O, quaternary NiCoFeCd-O, quaternary NiCoFeCr-O, and quinary NiCoFeCdCr-O. In \\u003cstrong\\u003eSupplementary Fig.\\u0026nbsp;30\\u003c/strong\\u003e, it is evident that the electronic structures of Ni and O are influenced by the incorporation of Cr in both quaternary NiCoFeCr-O and NiCoFeCdCr-O when compared to ternary NiCoFe-O and quaternary NiCoFeCd-O.The emergence of a peak at O1 position from the O 1s XPS spectrum is attributed to strong interactions between Cr and O, this Cr\\u0026ndash;O interaction may also affect the electronic structure of Ni.\\u003csup\\u003e\\u003cspan class=\\\"CitationRef\\\"\\u003e49\\u003c/span\\u003e, \\u003cspan class=\\\"CitationRef\\\"\\u003e50\\u003c/span\\u003e\\u003c/sup\\u003e Analysis of the Cr 2p, Co 2p, Fe 2p, and Cd 3d XPS spectra presented in \\u003cstrong\\u003eSupplementary Fig.\\u0026nbsp;31\\u003c/strong\\u003e and \\u003cstrong\\u003eS32\\u003c/strong\\u003e indicate that Cr exists as Cr\\u003csup\\u003e3+\\u003c/sup\\u003e, while Co, Fe, and Cd are present as Co\\u003csup\\u003e2+\\u003c/sup\\u003e, Fe\\u003csup\\u003e3+\\u003c/sup\\u003e, and Cd\\u003csup\\u003e2+\\u003c/sup\\u003e in NiCoFeCdCr-O respectively. Moreover, the high-resolution XPS spectra for ternary NiCoFe-O, quaternary NiCoFeCd-O, and NiCoFeCr-O demonstrate consistent valence states among these metal elements (\\u003cstrong\\u003eSupplementary Fig.\\u0026nbsp;33\\u003c/strong\\u003e), comparable to those observed in quinary NiCoFeCdCr-O, thereby indicating a similar structural configuration across samples synthesized via this strategy.\\u003c/p\\u003e\\n \\u003cp\\u003eThe electronic structure of the catalysts was further elucidated by X-ray Absorption Fine Structure (XAFS) analysis. Analysis of the X-ray absorption near-edge structure (XANES) presented in Fig. \\u003cspan class=\\\"InternalRef\\\"\\u003e4\\u003c/span\\u003ea, c, e, and \\u003cstrong\\u003ei\\u003c/strong\\u003e reveal that the adsorption edges of Ni, Co, Fe, and Cr K-edges in ternary NiCoFe-O, quaternary NiCoFeCd-O, quaternary NiCoFeCr-O, and quinary NiCoFeCdCr-O closely resemble those of NiO, Co\\u003csub\\u003e3\\u003c/sub\\u003eO\\u003csub\\u003e4\\u003c/sub\\u003e, \\u0026alpha;-Fe\\u003csub\\u003e2\\u003c/sub\\u003eO\\u003csub\\u003e3\\u003c/sub\\u003e and Cr\\u003csub\\u003e2\\u003c/sub\\u003eO\\u003csub\\u003e3\\u003c/sub\\u003e. This observation indicates that their oxidation states are analogous to those of the corresponding spinel oxides. Furthermore, the Cd K-edge XANES spectra elucidated the similar electron structure of Cd in quaternary NiCoFeCd-O and quinary NiCoFeCdCr-O. To further investigate the alterations in coordination configuration, an extended X-ray absorption fine structure (EXAFS) analysis was conducted. As illustrated in the Ni EXAFS spectra (Fig. \\u003cspan class=\\\"InternalRef\\\"\\u003e4\\u003c/span\\u003eb), the first shell EXAFS peak at 1.63 \\u0026Aring; corresponds to Ni-O scattering, while peaks at 2.55 \\u0026Aring; associated with Ni-M pathways. Notably, shorter Ni-O and Ni-M bond distances were recorded for samples incorporating other metals, indicating that metal incorporation induces changes in both Ni-O and Ni-M lengths.\\u003csup\\u003e\\u003cspan class=\\\"CitationRef\\\"\\u003e51\\u003c/span\\u003e\\u003c/sup\\u003e The first shell EXAFS peak observed at approximately 1.44 \\u0026Aring; is attributed to Co-O scattering (Fig. \\u003cspan class=\\\"InternalRef\\\"\\u003e4\\u003c/span\\u003ed). Peaks corresponding to Co-M1 and Co-M2 pathways were detected at 2.42 and 2.98 \\u0026Aring;, respectively. It is noteworthy that longer Co-O and Co-M bond distances were recorded for samples incorporating other metals, indicating that such metal incorporation leads to an increase in both Co-O and Co-M lengths.\\u003csup\\u003e\\u003cspan class=\\\"CitationRef\\\"\\u003e52\\u003c/span\\u003e\\u003c/sup\\u003e As illustrated in Fig. \\u003cspan class=\\\"InternalRef\\\"\\u003e4\\u003c/span\\u003ef, the first coordination shell EXAFS peak at 1.47 \\u0026Aring; corresponds to Fe-O scattering, while peaks at 2.52 \\u0026Aring; associated with Fe-M pathways were also identified.\\u003csup\\u003e\\u003cspan class=\\\"CitationRef\\\"\\u003e53\\u003c/span\\u003e\\u003c/sup\\u003e The shorter Fe-O bond and longer Fe-M bond are observed for samples incorporating other metals.\\u003csup\\u003e\\u003cspan class=\\\"CitationRef\\\"\\u003e54\\u003c/span\\u003e, \\u003cspan class=\\\"CitationRef\\\"\\u003e55\\u003c/span\\u003e\\u003c/sup\\u003e In Fig. \\u003cspan class=\\\"InternalRef\\\"\\u003e4\\u003c/span\\u003eh, NiCoFeCd-O exhibits Cd-O and Cd-M peak positions at 1.72 and 3.01 \\u0026Aring;, respectively. However, the Cr incorporation causes a dramatic decrease in Cd-O length and an increase in Cd-M. The Cr-O coordination is observed in Fig. \\u003cspan class=\\\"InternalRef\\\"\\u003e4\\u003c/span\\u003ej, suggesting the strong effect of Cr-O. Besides, contrasting with the M-O length, major changes in Ni-M, Co-M, Fe-M, Cd-M, and Cr-M bond lengths are observed in ternary NiCoFe-O, quaternary NiCoFeCd-O, quaternary NiCoFeCr-O, and quinary NiCoFeCdCr-O. Metal incorporation significantly alters the bond length of metal-metal and diminishes the intensity of the Cd/Cr-metal peaks. Importantly, similar results are further corroborated by the EXAFS analysis of NiCoFe-O, NiCoFeCd-O, NiCoFeCr-O, NiCoFeCdCrLa-O, NiCoFeCdCrLaSn-O, and NiCoFeCdCrLaSnZn-O (\\u003cstrong\\u003eSupplementary Fig.\\u0026nbsp;34\\u0026ndash;41\\u003c/strong\\u003e). Overall, the aforementioned characterization results suggest that the high-entropy system exhibits lattice distortion upon the incorporation of various elemental atoms, which modifies interatomic coordination and electronic structure, potentially resulting in exceptional catalytic activity. Bader charge analysis further offers insight into the varying numbers of transferred electrons at the active site for ternary NiCoFe-O, quaternary NiCoFeCd-O, quaternary NiCoFeCr-O, and quinary NiCoFeCdCr-O. It indicates that oxygen tends to accept electrons, whereas Fe and Cr are more prone to electron loss, with Cd exhibiting the least tendency to lose electrons. In comparison to NiCoFe-O, the number of electrons received by oxygen in NiCoFeCdCr-O appears to have decreased, suggesting that electron transfer may have occurred among different elements (Fig. \\u003cspan class=\\\"InternalRef\\\"\\u003e4\\u003c/span\\u003ek).\\u003c/p\\u003e\\n \\u003cp\\u003e\\u003cstrong\\u003ePerformance of Catalytic Hydrogenation for p-Nitrophenol.\\u003c/strong\\u003e As a proof of demonstration, the catalytic performance for quinary NiCoFeCdCr-O was explored as a catalyst for the catalytic hydrogenation of p-nitrophenol (4-NP). As illustrated in \\u003cstrong\\u003eSupplementary Fig.\\u0026nbsp;42a\\u003c/strong\\u003e, the aqueous solution of 4-NP exhibits an absorption peak at approximately 317 nm.\\u003csup\\u003e\\u003cspan class=\\\"CitationRef\\\"\\u003e56\\u003c/span\\u003e\\u003c/sup\\u003e The introduction of sodium borohydride leads to the appearance of a new absorption peak around 400 nm. Following the addition of the catalyst to the solution, a decrease in the absorbance of 4-NP is observed, accompanied by the emergence of a distinct peak near 310 nm, which corresponds to 4-aminophenol (4-AP). Figure \\u003cspan class=\\\"InternalRef\\\"\\u003e5\\u003c/span\\u003ea illustrates the typical absorbance changes of 4-NP during the reactions conducted at 25\\u0026deg;C. The NiCoFeCdCr-O catalyst achieves a remarkable 100% conversion efficiency of 4-NP within 150 seconds, which is superior to ternary NiCoFe-O, quaternary NiCoFeCd-O, and quaternary NiCoFeCr-O in \\u003cstrong\\u003eSupplementary Fig.\\u0026nbsp;42b-d\\u003c/strong\\u003e. Furthermore, a linear relationship is established in Fig. \\u003cspan class=\\\"InternalRef\\\"\\u003e5\\u003c/span\\u003eb by fitting the values of ln(C\\u003csub\\u003et\\u003c/sub\\u003e/C\\u003csub\\u003e0\\u003c/sub\\u003e) against the corresponding reaction time, which aligns with first-order kinetic behavior. Consequently, the calculated apparent rate constant (\\u003cem\\u003ek\\u003c/em\\u003e) for NiCoFeCdCr-O was 1.79 min\\u003csup\\u003e\\u0026minus;\\u0026thinsp;1\\u003c/sup\\u003e (Fig. \\u003cspan class=\\\"InternalRef\\\"\\u003e5\\u003c/span\\u003ec), which is 7.40, 2.82, and 1.79 times that of NiCoFe-O (0.242 min\\u003csup\\u003e\\u0026minus;\\u0026thinsp;1\\u003c/sup\\u003e), NiCoFeCd-O (0.635 min\\u003csup\\u003e\\u0026minus;\\u0026thinsp;1\\u003c/sup\\u003e) and NiCoFeCr-O (1.00 min\\u003csup\\u003e\\u0026minus;\\u0026thinsp;1\\u003c/sup\\u003e), respectively. Moreover, NiCoFeCdCr-O exhibited a high specific constant (\\u003cem\\u003eK\\u003c/em\\u003e) of 1.53\\u0026times;10\\u003csup\\u003e6\\u003c/sup\\u003e min\\u003csup\\u003e\\u0026minus;\\u0026thinsp;1\\u003c/sup\\u003e g\\u003csup\\u003e\\u0026minus;\\u0026thinsp;1\\u003c/sup\\u003e. As illustrated in Fig. \\u003cspan class=\\\"InternalRef\\\"\\u003e5\\u003c/span\\u003ed, \\u003cstrong\\u003eSupplementary Table\\u0026nbsp;2\\u003c/strong\\u003e, and \\u003cstrong\\u003eSupplementary Table\\u0026nbsp;3\\u003c/strong\\u003e, NiCoFeCdCr-O outperforms most reported noble metal-based catalysts and high-entropy materials for the direct hydrogenation of 4-NP. Furthermore, a linear relationship can be derived by fitting the value of ln(C\\u003csub\\u003et\\u003c/sub\\u003e/C\\u003csub\\u003e0\\u003c/sub\\u003e) under the various reaction temperatures in Fig. \\u003cspan class=\\\"InternalRef\\\"\\u003e5\\u003c/span\\u003ee. The values of the \\u003cem\\u003ek\\u003c/em\\u003e demonstrated an increase with elevated reaction temperatures, this observation can be explained by collision theory. As the system temperature rises, the intense motion of catalyst and 4-NP increases the likelihood of collisions, resulting in faster reaction rates. The final activation energy for NiCoFeCdCr-O was calculated to be 49.7 kJ/mol from the calculated \\u003cem\\u003ek\\u003c/em\\u003e at different reaction temperatures using the Arrhenius equation. The lower the activation energy indicates the less energy required for the reaction, which is more conducive to the reaction.\\u003csup\\u003e\\u003cspan class=\\\"CitationRef\\\"\\u003e57\\u003c/span\\u003e, \\u003cspan class=\\\"CitationRef\\\"\\u003e58\\u003c/span\\u003e\\u003c/sup\\u003e Additionally, the performance of various 4-NP concentrations was evaluated to assess the catalytic suitability of the catalyst (\\u003cstrong\\u003eSupplementary Fig.\\u0026nbsp;43\\u003c/strong\\u003e). Reusability is widely recognized as a critical parameter for catalysts. As illustrated in Fig. \\u003cspan class=\\\"InternalRef\\\"\\u003e5\\u003c/span\\u003ef, the NiCoFeCdCr-O catalyst exhibited sustained high activity over 10 cycles, with the conversion rate consistently maintained above 95%. These findings indicate that the NiCoFeCdCr-O catalyst not only demonstrates high catalytic activity but also exhibits excellent recyclability. To further explore the general applicability of the NiCoFeCdCr-O catalyst in the reduction of nitrophenolic pollutants to aminophenol, a range of nitrophenol with diverse structures was selected as probe molecules, including 2-nitrophenol (2-NP) and 3-nitrophenol (3-NP). As illustrated in \\u003cstrong\\u003eSupplementary Fig.\\u0026nbsp;44\\u003c/strong\\u003e, a series of successive UV\\u0026ndash;vis spectra clearly demonstrates that the NiCoFeCdCr-O catalyst facilitates the reduction of nitrophenol to their corresponding aminophenol products in the presence of NaBH\\u003csub\\u003e4\\u003c/sub\\u003e.\\u003c/p\\u003e\\n \\u003cp\\u003eIn order to illustrate the superiority of the coordinating etching and precipitating method, NiCoFeCdCrO\\u003csub\\u003eNaOH\\u003c/sub\\u003e was synthesized with NaOH solution instead of Na\\u003csub\\u003e2\\u003c/sub\\u003eS\\u003csub\\u003e2\\u003c/sub\\u003eO\\u003csub\\u003e3\\u003c/sub\\u003e solution, and other synthesis and testing conditions remained unchanged. As shown in \\u003cstrong\\u003eSupplementary Fig.\\u0026nbsp;45a\\u003c/strong\\u003e, the catalytic activity of NiCoFeCdCrO\\u003csub\\u003eNaOH\\u003c/sub\\u003e exhibits a precipitous decline with 4-NP being entirely degraded for more than 40 minutes. The XRD results of NiCoFeCdCrO\\u003csub\\u003eNaOH\\u003c/sub\\u003e revealed the presence of the CuO phase, indicating that Cu₂O is not completely consumed and converted into CuO following thermal treatment (\\u003cstrong\\u003eSupplementary Fig.\\u0026nbsp;45b\\u003c/strong\\u003e). The findings indicate that CuO demonstrated inert catalytic activity. To verify this hypothesis, the pure CuO was obtained by direct thermal treatment of pure Cu\\u003csub\\u003e2\\u003c/sub\\u003eO. The performance test of pure CuO demonstrated that the catalytic activity was inferior to that of NiCoFeCdCrO\\u003csub\\u003eNaOH\\u003c/sub\\u003e (\\u003cstrong\\u003eSupplementary Fig.\\u0026nbsp;45c\\u003c/strong\\u003e). Additionally, the XRD patterns indicated the formation of a pure CuO phase with high crystallinity (\\u003cstrong\\u003eSupplementary Fig.\\u0026nbsp;45d\\u003c/strong\\u003e), therefore, which was consistent with the aforementioned hypothesis. In essence, the coordinating etchant method ensures the overwhelming consumption of Cu\\u003csub\\u003e2\\u003c/sub\\u003eO and circumvents large residues of CuO, thereby conferring upon the hollow nanocube NiCoFeCdCr-O a dominant role in the catalytic process.\\u003c/p\\u003e\\n\\u003c/div\\u003e\"},{\"header\":\"Conclusion\",\"content\":\"\\u003cp\\u003eIn summary, we have established a library of multicomponent hollow nanocube high-entropy spinel oxides, spanning ternary to octonary compositions, synthesized through the template-assisted route inspired by coordinating etching. Our detailed investigations into the underlying synthetic mechanisms elucidate that the formation of high-entropy spinel oxides transpires via four pivotal steps: (1) The preparation of the nanocube Cu\\u003csub\\u003e2\\u003c/sub\\u003eO temple, (2) the liberation of hydroxide ions (OH\\u003csup\\u003e\\u0026minus;\\u003c/sup\\u003e) through coordinating etching reactions between soft bases and soft acids; (3) The co-precipitation of various metal cations onto the nanocube shell, leading to the formation of high-entropy metal hydroxide (HE-OH); and (4) subsequent thermal treatment of HE-OH. Experimental results indicate that the formation and stabilization of HEO nanocubes are critically dependent on the generation of HE-OH, which is achieved by meticulously controlling the balance between the precipitation rate of metal hydroxides and the synchronous coordinating etching rate towards the soft acid. Furthermore, the DFT simulation reveals a more continuous DOS near the Fermi level and a more moderate d-band center for the representative quinary NiCoFeCdCr-O hollow nanocube. Consequently, in the catalytic hydrogenation of 4-NP, this quinary NiCoFeCdCr-O demonstrates exceptional catalytic activity and cyclic stability. The proposed synthesis methodology establishes a comprehensive platform for the advancement of HEOs.\\u003c/p\\u003e\"},{\"header\":\"Methods\",\"content\":\"\\u003cp\\u003e \\u003cb\\u003eReagents.\\u003c/b\\u003e Cupric sulfate pentahydrate (CuSO\\u003csub\\u003e4\\u003c/sub\\u003e, 99%), sodium hydroxide (NaOH, 98%), L(+)-Ascorbic acid (99.7%), ethanol absolute (CH\\u003csub\\u003e3\\u003c/sub\\u003eCH\\u003csub\\u003e2\\u003c/sub\\u003eOH), nickel chloride hexahydrate (NiCl\\u003csub\\u003e2\\u003c/sub\\u003e\\u0026middot;6H\\u003csub\\u003e2\\u003c/sub\\u003eO, 98%), cobalt chloride hexahydrate (CoCl\\u003csub\\u003e2\\u003c/sub\\u003e\\u0026middot;6H\\u003csub\\u003e2\\u003c/sub\\u003eO, 99%), ferrous sulfate (FeSO\\u003csub\\u003e4\\u003c/sub\\u003e\\u0026middot;7H\\u003csub\\u003e2\\u003c/sub\\u003eO, 99%), cadmium chloride hemi(pentahydrate) (CdCl\\u003csub\\u003e2\\u003c/sub\\u003e\\u0026middot;2.5H\\u003csub\\u003e2\\u003c/sub\\u003eO, 99%), chromic nitrate nonahydrate (Cr(NO\\u003csub\\u003e3\\u003c/sub\\u003e)\\u003csub\\u003e3\\u003c/sub\\u003e\\u0026middot;9H\\u003csub\\u003e2\\u003c/sub\\u003eO, 99%), lanthanum nitrate hydrate (La(NO\\u003csub\\u003e3\\u003c/sub\\u003e)\\u003csub\\u003e3\\u003c/sub\\u003e\\u0026middot;nH\\u003csub\\u003e2\\u003c/sub\\u003eO), stannous chloride dihydrate (SnCl\\u003csub\\u003e2\\u003c/sub\\u003e\\u0026middot;2H\\u003csub\\u003e2\\u003c/sub\\u003eO, 98%), zinc chloride (ZnSO\\u003csub\\u003e4\\u003c/sub\\u003e\\u0026middot;7H\\u003csub\\u003e2\\u003c/sub\\u003eO, 98%), polyvinylpyrrolidone K-30 (PVP K-30, 99%), sodium thiosulfate (NaS\\u003csub\\u003e2\\u003c/sub\\u003eO\\u003csub\\u003e3\\u003c/sub\\u003e\\u0026middot;5H\\u003csub\\u003e2\\u003c/sub\\u003eO, 99%), p-nitrophenol (4-NP, analytical grade,), 3-nitrophenol (3-NP, 99%), 2-nitrophenol (2-NP, 99%), sodium borohydride (NaBH\\u003csub\\u003e4\\u003c/sub\\u003e, 98%) and sodium citrate were used without any further purification.\\u003c/p\\u003e \\u003cp\\u003e \\u003cb\\u003eSynthesis of HEOs.\\u003c/b\\u003e The dried HE-OH was annealed in a tube oven at 600℃ for 2 h. Additionally, the NiCoFeCd-O, NiCoFeCr-O, and NiCoFe-O were synthesized by the same synthetic route without adding Cr or Cd. The NiCoFeCdCrLa-O, NiCoFeCdCrLaSn-O, and NiCoFeCdCrLaSnZn-O were synthesized by the same synthetic route with the addition of La(NO\\u003csub\\u003e3\\u003c/sub\\u003e)\\u003csub\\u003e3\\u003c/sub\\u003e\\u0026middot;nH\\u003csub\\u003e2\\u003c/sub\\u003eO (4.9 mg), SnCl\\u003csub\\u003e2\\u003c/sub\\u003e\\u0026middot;2H\\u003csub\\u003e2\\u003c/sub\\u003eO (3.4 mg), and ZnSO\\u003csub\\u003e4\\u003c/sub\\u003e\\u0026middot;7H\\u003csub\\u003e2\\u003c/sub\\u003eO (4.3 mg). The NiCoFeCdCrO\\u003csub\\u003eNaOH\\u003c/sub\\u003e were synthesized by the same synthetic route with Na\\u003csub\\u003e2\\u003c/sub\\u003eS\\u003csub\\u003e2\\u003c/sub\\u003eO\\u003csub\\u003e3\\u003c/sub\\u003e replaced by NaOH.\\u003c/p\\u003e \\u003cp\\u003e \\u003cb\\u003eCatalytic reduction of p-nitrophenol.\\u003c/b\\u003e Typically, NaBH\\u003csub\\u003e4\\u003c/sub\\u003e (0.1898 g) was dissolved into 20 mL ultrapure water, and then NaBH\\u003csub\\u003e4\\u003c/sub\\u003e aqueous solution was added into the 20 mL of 2 mM 4-NP to make the concentration of 4-NP to be 1 mM in the catalytic system. Then, after stirring for 5 min, 20 \\u0026micro;L of catalyst suspension (2 mg/mL) was injected quickly into the system of 4-NP and NaBH\\u003csub\\u003e4\\u003c/sub\\u003e to cause the hydrogenation reaction. Subsequently, 0.5 ml solution from the system was diluted to 10 ml during the reaction process at regular intervals (30 s) and then monitored through a UV\\u0026ndash;vis spectrometer. The catalyst was separated by the filtration device and dried after the reduction reaction had finished, and then the performance test was carried out again with other experimental conditions that remained unchanged for recyclability experiments with ten successive runs.\\u003c/p\\u003e \\u003cp\\u003eln(C\\u003csub\\u003et\\u003c/sub\\u003e/C\\u003csub\\u003e0\\u003c/sub\\u003e)\\u0026thinsp;=\\u0026thinsp;ln(A\\u003csub\\u003et\\u003c/sub\\u003e/A\\u003csub\\u003e0\\u003c/sub\\u003e) = -\\u003cem\\u003ek\\u003c/em\\u003et,\\u003c/p\\u003e \\u003cp\\u003eWhere \\u003cem\\u003ek\\u003c/em\\u003e is the apparent rate constant, t is the reaction time, C\\u003csub\\u003et\\u003c/sub\\u003e (A\\u003csub\\u003et\\u003c/sub\\u003e) and C\\u003csub\\u003e0\\u003c/sub\\u003e (A\\u003csub\\u003e0\\u003c/sub\\u003e) are defined as the concentrations (absorbances) of 4-NP at time t and t\\u0026thinsp;=\\u0026thinsp;0, respectively.\\u003c/p\\u003e \\u003cp\\u003e \\u003cem\\u003eK\\u0026thinsp;=\\u0026thinsp;k\\u003c/em\\u003e/m\\u003csub\\u003emetal\\u003c/sub\\u003e,\\u003c/p\\u003e \\u003cp\\u003ewhere \\u003cem\\u003eK\\u003c/em\\u003e is the ratio rate constant, m\\u003csub\\u003emetal\\u003c/sub\\u003e is the weight of the metal in the used catalyst.\\u003c/p\\u003e \\u003cp\\u003eConversion = (C\\u003csub\\u003e0\\u003c/sub\\u003e-C\\u003csub\\u003et\\u003c/sub\\u003e)/C\\u003csub\\u003e0\\u003c/sub\\u003e*100%, where C\\u003csub\\u003e0\\u003c/sub\\u003e is the initial absorption and C\\u003csub\\u003et\\u003c/sub\\u003e is the final absorption at a desired interval of time, t.\\u003c/p\\u003e \\u003cp\\u003eThe activation energy for the reduction of p-nitrophenol could be calculated according to the Arrhenius equation:\\u003c/p\\u003e \\u003cp\\u003eln\\u003cem\\u003ek\\u003c/em\\u003e = -E\\u003csub\\u003ea\\u003c/sub\\u003e/RT\\u0026thinsp;+\\u0026thinsp;lnA, where R is the ideal gas constant (equals to 8.314 J mol\\u003csup\\u003e\\u0026minus;\\u0026thinsp;1\\u003c/sup\\u003e K\\u003csup\\u003e\\u0026minus;\\u0026thinsp;1\\u003c/sup\\u003e), A is the index factor, and the slope of the logarithmic plot of rate constant (\\u003cem\\u003ek\\u003c/em\\u003e) and T\\u003csup\\u003e\\u0026minus;\\u0026thinsp;1\\u003c/sup\\u003e can be indicated as -E\\u003csub\\u003ea\\u003c/sub\\u003e/R.\\u003c/p\\u003e\"},{\"header\":\"Declarations\",\"content\":\"\\u003cp\\u003e\\u003cstrong\\u003eData availability\\u003c/strong\\u003e\\u003c/p\\u003e\\n\\u003cp\\u003eThe data supporting the findings of this study are available within the article and its Supplementary Information files. All other relevant source data are available from the corresponding authors upon reasonable request.\\u003c/p\\u003e\\n\\u003cp\\u003e\\u003cstrong\\u003eAcknowledgments\\u003c/strong\\u003e\\u003c/p\\u003e\\n\\u003cp\\u003eThis work was supported by National Natural Science Founda-tion of China (Grants No. U22A20143, 22201262, 22375019), Beijing Institute of Technology Research Fund Program for Young Scholars (2022CX01011). The authors thank the Center for Advanced Analysis and Gene Sequencing of Zhengzhou University and the BL14W1 in the Shanghai Synchrotron Radiation Facility for help with characterizations.\\u0026nbsp;\\u003c/p\\u003e\\n\\u003cp\\u003e\\u003cstrong\\u003eAuthor Contributions\\u003c/strong\\u003e\\u003c/p\\u003e\\n\\u003cp\\u003eH.S. and W.C. conceived the idea, designed the study and wrote the paper. N.Z, Y.L. performed the sample synthesis, performed most of the reactions, collected and analyzed the data, and wrote the paper. W.C. and Z.S. carried out the X-ray absorption fine structure characterizations and data analysis. Y.L., L.Z and X.W. conducted the performance measurements. H.S. Z.Z., Y.Z., X.X. and B.Z. helped to check and revise the paper.\\u003c/p\\u003e\\n\\u003cp\\u003e\\u003cstrong\\u003eCompeting interests\\u003c/strong\\u003e\\u003c/p\\u003e\\n\\u003cp\\u003eThe authors declare no competing interests.\\u003c/p\\u003e\\n\\u003cp\\u003e\\u003cstrong\\u003eAdditional information\\u003c/strong\\u003e\\u003c/p\\u003e\\n\\u003cp\\u003eSupplementary information is available for this paper\\u003c/p\\u003e\\n\\u003cp\\u003eCorrespondence and requests for materials should be addressed to H.S or N.Z or W.C.\\u003c/p\\u003e\"},{\"header\":\"References\",\"content\":\"\\u003col\\u003e\\n\\u003cli\\u003eSarkar A\\u003cem\\u003e, et al.\\u003c/em\\u003e High entropy oxides for reversible energy storage. \\u003cem\\u003eNat. 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Commun.\\u003c/em\\u003e\\u003cstrong\\u003e15\\u003c/strong\\u003e, 5143 (2024).\\u003c/li\\u003e\\n\\u003c/ol\\u003e\"}],\"fulltextSource\":\"\",\"fullText\":\"\",\"funders\":[],\"hasAdminPriorityOnWorkflow\":false,\"hasManuscriptDocX\":true,\"hasOptedInToPreprint\":true,\"hasPassedJournalQc\":\"\",\"hasAnyPriority\":true,\"hideJournal\":false,\"highlight\":\"\",\"institution\":\"\",\"isAcceptedByJournal\":true,\"isAuthorSuppliedPdf\":false,\"isDeskRejected\":\"\",\"isHiddenFromSearch\":false,\"isInQc\":false,\"isInWorkflow\":false,\"isPdf\":false,\"isPdfUpToDate\":true,\"isWithdrawnOrRetracted\":false,\"journal\":{\"display\":true,\"email\":\"info@researchsquare.com\",\"identity\":\"nature-portfolio\",\"isNatureJournal\":true,\"hasQc\":false,\"allowDirectSubmit\":false,\"externalIdentity\":\"\",\"sideBox\":\"\",\"snPcode\":\"\",\"submissionUrl\":\"\",\"title\":\"Nature Portfolio\",\"twitterHandle\":\"\",\"acdcEnabled\":false,\"dfaEnabled\":false,\"editorialSystem\":\"ejp\",\"reportingPortfolio\":\"\",\"inReviewEnabled\":true,\"inReviewRevisionsEnabled\":false},\"keywords\":\"\",\"lastPublishedDoi\":\"10.21203/rs.3.rs-6092386/v1\",\"lastPublishedDoiUrl\":\"https://doi.org/10.21203/rs.3.rs-6092386/v1\",\"license\":{\"name\":\"CC BY 4.0\",\"url\":\"https://creativecommons.org/licenses/by/4.0/\"},\"manuscriptAbstract\":\"\\u003cp\\u003eHigh-entropy oxides (HEOs) consist of multiple principal metal cations and oxygen anions, which enhances compositional versatility and promotes the emergence of atypical properties within oxide materials. Nonetheless, precisely shaping HEOs in hollow nanostructures remains a significant challenge due to the disparate nucleation and growth kinetics of the various metal oxide compositions in HEOs. Herein, we present a general strategy for the versatile synthesis of multicomponent hollow nanocubes HEOs libraries from ternary to octonary. A template-assisted route inspired by coordinating etching was utilized for the synthesis of HEOs hollow nanocubes through meticulous selection of the coordinating etchant and optimization of the reaction conditions. This distinctive approach demonstrates the potential for precisely designing high-quality HEOs hollow nanocubes with diverse compositions at room temperature, which potentially manifest promising prospects for various applications.\\u003c/p\\u003e\",\"manuscriptTitle\":\"Coordinating Etching Inspired Synthesis of noble-metal-free monodisperse high-entropy oxides hollow nanocubes libraries\",\"msid\":\"\",\"msnumber\":\"\",\"nonDraftVersions\":[{\"code\":1,\"date\":\"2025-03-04 07:20:44\",\"doi\":\"10.21203/rs.3.rs-6092386/v1\",\"editorialEvents\":[],\"status\":\"published\",\"journal\":{\"display\":true,\"email\":\"info@researchsquare.com\",\"identity\":\"nature-communications\",\"isNatureJournal\":true,\"hasQc\":false,\"allowDirectSubmit\":false,\"externalIdentity\":\"NCOMMS\",\"sideBox\":\"Learn more about [Nature Communications](http://www.nature.com/ncomms/)\",\"snPcode\":\"\",\"submissionUrl\":\"https://mts-ncomms.nature.com/\",\"title\":\"Nature Communications\",\"twitterHandle\":\"\",\"acdcEnabled\":true,\"dfaEnabled\":true,\"editorialSystem\":\"ejp\",\"reportingPortfolio\":\"Nature Communications\",\"inReviewEnabled\":true,\"inReviewRevisionsEnabled\":false}}],\"origin\":\"\",\"ownerIdentity\":\"07d04020-e053-40c3-9066-edba587a1ac9\",\"owner\":[],\"postedDate\":\"March 4th, 2025\",\"published\":true,\"recentEditorialEvents\":[],\"rejectedJournal\":[],\"revision\":\"\",\"amendment\":\"\",\"status\":\"published-in-journal\",\"subjectAreas\":[{\"id\":45040331,\"name\":\"Physical sciences/Materials science/Materials for energy and catalysis\"},{\"id\":45040332,\"name\":\"Physical sciences/Materials science/Nanoscale materials\"}],\"tags\":[],\"updatedAt\":\"2025-11-07T08:09:03+00:00\",\"versionOfRecord\":{\"articleIdentity\":\"rs-6092386\",\"link\":\"https://doi.org/10.1038/s41467-025-64796-y\",\"journal\":{\"identity\":\"nature-communications\",\"isVorOnly\":false,\"title\":\"Nature Communications\"},\"publishedOn\":\"2025-11-06 05:00:00\",\"publishedOnDateReadable\":\"November 6th, 2025\"},\"versionCreatedAt\":\"2025-03-04 07:20:44\",\"video\":\"\",\"vorDoi\":\"10.1038/s41467-025-64796-y\",\"vorDoiUrl\":\"https://doi.org/10.1038/s41467-025-64796-y\",\"workflowStages\":[]},\"version\":\"v1\",\"identity\":\"rs-6092386\",\"journalConfig\":\"researchsquare\"},\"__N_SSP\":true},\"page\":\"/article/[identity]/[[...version]]\",\"query\":{\"redirect\":\"/article/rs-6092386\",\"identity\":\"rs-6092386\",\"version\":[\"v1\"]},\"buildId\":\"8U1c8b4HqxoKbykW_rLl7\",\"isFallback\":false,\"isExperimentalCompile\":false,\"dynamicIds\":[84888],\"gssp\":true,\"scriptLoader\":[]}","source_license":"CC-BY-4.0","license_restricted":false}