Startseite Coupling the vanadium-induced amorphous/crystalline NiFe2O4 with phosphide heterojunction toward active oxygen evolution reaction catalysts
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Coupling the vanadium-induced amorphous/crystalline NiFe2O4 with phosphide heterojunction toward active oxygen evolution reaction catalysts

  • Hanpeng Deng , Hunan Jiang , Kun Wang , Zhenyu Wang , Bin Wang , Zuowan Zhou und Jinyang Li EMAIL logo
Veröffentlicht/Copyright: 25. November 2022
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Nanotechnology Reviews
Aus der Zeitschrift Nanotechnology Reviews Band 11 Heft 1

Abstract

Developing efficient and robust electrocatalysts is increasingly essential for water splitting, severely hindered by the sluggish four-electron transfer process of oxygen evolution reaction (OER). Amorphous/crystalline heterophase engineering has recently emerged as a promising electronic modulation approach for OER catalysts but suffers from poor conductivity of the amorphous structure. Here, we coupled the amorphous/crystalline NiFe2O4 induced by vanadium doping with NiP heterojunction, highlighting the synergistic effect in modulating the electronic structures and the complementary effect in promoting conductivity. As a superior electrocatalyst to commercial RuO2, the as-prepared NFO-V0.3-P showed a low overpotential of 277 mV at the current density of 20 mA cm−2, a Tafel slope of 45 mV dec−1, and long-term stability. The excellent OER catalytic activity is attributed to the synergistic effect at the heterophase interface with rich active sites, fine-tuning of electronic regulation, and enhanced conductivity.

Keywords: spinel oxide; OER; electrocatalyst; doping; heterojunction; heterophase

1 Introduction

Electrolysis of water to produce hydrogen and oxygen is a promising approach to solving current energy crisis and environmental pollution problems [1,2,3]. The bottleneck of electrochemical water splitting is the slow oxygen evolution reaction (OER) on the anode [4], while the commonly used noble metal iridium (Ir)-based and ruthenium (Ru)-based catalysts are limited by their high cost and poor stability [5,6,7]. Therefore, the development of earth-abundant transition metals as high-performance OER electrocatalysts has attracted more and more researchers’ attention [8,9,10]. For example, spinel nickel ferrite NiFe2O4 has become a promising catalyst due to its advantages such as low cost, easy preparation, and easy structure control [11]. Researchers have prepared a series of NiFe2O4 catalysts with different structures and properties by hydrothermal method [12], solvothermal method [13], and sol–gel method [14]. However, pure NiFe2O4 is not suitable for OER due to the shortcomings of active sites and electronic structure and needs to be modified [15]. There are two main strategies to prepare transition metals into high-performance OER catalysts. The first is to adjust the morphology, geometry, and size of materials to increase the number of active centers [16,17,18]. The second is to improve the intrinsic activity of each active center by adjusting the crystal and electronic structures [19,20,21].

Doping can lead to heterophase, exhibiting optimized catalytic activity [22,23]. Recently, it has been reported that doping can induce the formation of amorphous/crystalline heterophase, resulting in abundant surface defects and coordinatively unsaturated sites, thereby increasing the exposure of active sites [24]. Han et al. fabricated F-doped Co2B with a high-density crystalline/amorphous interface that significantly enhances OER activity [25]. V is favored among all the dopants due to its low cost and robust existence in various valence states [26]. Li et al. reported that V promoted the transfer of electrons from Ni to VO x and reduced the adsorption energy; VO x also led to significant decay of the Ni lattice, resulting in amorphous/crystalline heterophase with increased electrochemically active surface area [27]. However, the low electrical conductivity of the amorphous structure severely limits the charge transfer during catalysis [28]. The built-in electric field at the heterojunction interface promotes charge transfer and redistribution, effectively regulating the electronic structure and enhancing conductivity [29]. Thus, heterojunction might be a remedy for the amorphous/crystalline structure. Furthermore, although spinel oxides have been intensively reported previously, the amorphous/crystalline heterophase spinel oxides coupled with phosphide heterojunction have not been reported yet. Therefore, it is desirable to construct such a hybrid interface and investigate the synergistic electronic regulation effect for boosting OER.

Based on the above challenges, we combined V-doping and phosphide heterojunction strategies to construct an amorphous/crystalline heterophase catalyst NFO-V0.3-P to synergistically optimize the electrical structure and conductivity for OER. The introduction of V weakened the crystallization ability of spinel NiFe2O4 and induced the formation of amorphous/crystalline heterophase with abundant oxygen vacancies and uncoordinated sites. Although V doping alone promoted the rearrangement of the electronic structure, the addition of NiP heterostructure improved the amorphous phase’s poor conductivity and further optimized the electronic structure by reducing the e g occupancy of Ni to be around 1.2. The as-prepared NFO-V0.3-P achieved a low overpotential of 277 mV at the current density of 20 mA cm−2, a Tafel slope of 45 mV dec−1, and long-term stability in alkaline media. This work provides an insightful coupling strategy for designing advanced OER electrocatalysts and performs a practical evaluation from the perspective of the e g occupancy in revealing its potential in synergistic electronic regulation.

2 Experimental

2.1 Materials

Nickel nitrate hexahydrate (Ni(NO3)2·6H2O, analytically pure), iron(iii) nitrate nonahydrate (Fe(NO3)3·9H2O, analytically pure), hexadecyl trimethyl ammonium bromide (CTAB, >98%), vanadium(iii) chloride (VCl3, >97%), ammonia (NH3·H2O, analytically pure), sodium hypophosphite (NaH2PO2, analytically pure), potassium hydroxide (KOH, analytically pure) were purchased from Kelong Chemical Agent. Ruthenium oxide (RuO2, 99.95%) was purchased from Alfa Aeser. Nafion solution (5%) was purchased from Dupont. All chemicals were used as received without further purification.

2.2 Synthesis of NFO electrocatalyst

First, Ni(NO3)2·6H2O (1 mmol), Fe(NO3)3·9H2O (2 − x mmol), and CTAB (0.2 g) were dissolved in a mixed solution of 20 mL deionized water and 10 mL ethanol and stirred for 1 h to obtain a homogeneous solution. Then, NH3·H2O (3 mL) was added dropwise under vigorous stirring. Subsequently, the solution was transferred to a 50 mL Teflon-lined autoclave and heated at 180°C for 12 h. The precipitate was collected by centrifugation, washed with ethanol and water, and dried at 50°C overnight. Finally, the precursor was ground and calcined in a muffle furnace at 400°C for 4 h to obtain the NFO catalyst.

2.3 Synthesis of NFO-V x electrocatalysts

Except for the raw materials, the preparation method of NFO-V x (x = 0.1, 0.3, 0.5) catalysts is the same as that of NFO. First, Ni(NO3)2·6H2O (1 mmol), Fe(NO3)3·9H2O (2 − x mmol), VCl3 (x mmol), and CTAB (0.2 g) were dissolved in a mixed solution of 20 mL deionized water and 10 mL ethanol and stirred for 1 h to obtain a homogeneous solution. The following preparation steps are exactly the same as that of NFO catalyst, and finally, the NFO-V x (x = 0.1, 0.3, 0.5) catalysts were obtained.

2.4 Synthesis of NFO-Vx-P electrocatalyst

The prepared NFO-V0.3 and NaH2PO2 were loaded in two porcelain boats with a mass ratio of 1:3 and were placed downstream and upstream of the tube furnace, respectively. The NFO-V0.3-P catalyst was prepared by heating to 300°C at a heating rate of 2°C min−1 under an Ar atmosphere for 2 h.

2.5 Material characterizations

The phase structure of the catalysts was determined using an X’pert Pro powder X-ray diffraction (XRD) from 20° to 80°. Scanning electron microscopy (SEM) images and elemental mapping were obtained using a JEOL JSM-7800 F field-emission SEM. Transmission electron microscope (TEM) images were taken using a Tecnai G220 (S-TWIN, FEI). X-ray photoelectron spectroscopy (XPS) was measured by Thermo ESCALAB 250XI. Electron paramagnetic resonance (EPR) spectra were obtained using a Bruker EMX plus X-band EPR spectrometer.

2.6 Electrochemical measurements

Electrochemical measurements were performed on Ivium Vertex. C electrochemical workstation in a three-electrode electrochemical cell. Pt sheet and Hg/HgO were used as the counter electrode and reference electrode. 1 M KOH solution was used as the electrolyte; 5 mg of catalyst was ultrasonically dispersed in a mixed solution of ethanol (900 μL) and Nafion (5 wt%, 100 μL) to obtain a homogeneous catalyst ink. Then, 100 µL of the as-prepared ink was drop cast onto nickel foam (1 cm × 1 cm) to prepare the working electrode with a catalyst loading of 0.5 mg cm−2.

The electrolyte was bubbled with O2 for 30 min before the OER measurements and maintained an O2-saturated electrolyte throughout the measurement. Cyclic voltammetry (CV) between 0 and 1 V vs Hg/HgO at a scan rate of 50 mV s−1 was performed to activate the catalysts surface until a steady-state CV curve was established. Linear sweep voltammetry (LSV) curves were collected at a scan rate of 5 mV s−1 and corrected by solution resistance (R s). Electrochemical impedance spectroscopy (EIS) was performed at open circuit potential over the frequency range between 100 kHz and 0.1 Hz. By calibrating the reference electrode (Figure S1), all potential values were calibrated concerning the reversible hydrogen electrode (RHE) by E RHE  =  E Hg/HgO + 0.93 V. Overpotentials (η) was calculated based on the formula η  =  E RHE − 1.23 V. Electrochemical active surface areas (ECSA) were obtained by measuring electrochemical double-layer capacitance (C dl) of catalysts. Chronopotentiometry measurements evaluated stability at the current density of 20 and 100 mA cm−2.

3 Results and discussion

3.1 Characterization analysis of catalysts

The synthesis of the NFO-V0.3-P catalyst involved two steps. As shown in Figure 1, the first step was to dope V into the catalyst by hydrothermal method. CTAB as a surfactant modulated the shape and size of nanoparticles and prevented excessive aggregation of nanoparticles. After the first heat treatment, transition metal oxide nanoparticles with the structural formula of NiV0.3Fe1.7O4 were prepared and denoted as NFO-V0.3. In the second step, a small amount of NaH2PO2 was pyrolyzed in a tube furnace to grow metal phosphide on the catalyst surface to obtain the final catalyst, which was named NFO-V0.3-P. V and P have been successfully introduced into the catalyst system in the corresponding steps, as shown in Figure 2(a) and Figures S2, S3. The distribution of each element in the catalyst is uniform.

Figure 1 Catalyst preparation process diagram.
Figure 1

Catalyst preparation process diagram.

Figure 2 (a) SEM image and the corresponding elemental mapping of NFO-V0.3-P. (b) XRD patterns of NFO, NFO-V0.3, NFO-V0.3-P. (c–e) TEM and (f–h) HRTEM image of NFO, NFO-V0.3, NFO-V0.3-P.
Figure 2

(a) SEM image and the corresponding elemental mapping of NFO-V0.3-P. (b) XRD patterns of NFO, NFO-V0.3, NFO-V0.3-P. (c–e) TEM and (f–h) HRTEM image of NFO, NFO-V0.3, NFO-V0.3-P.

The catalysts’ morphology and crystal structure evolution after V introduction and surface partial phosphating were characterized using XRD and TEM. As shown in Figure 2(b) and Figure S4, the diffraction angles and diffraction intensity of the NFO catalyst are consistent with those of NiFe2O4 (PDF #10-0325), indicating the successful preparation of an inverse spinel transition metal oxide with the good crystal structure. The catalyst after V doping also shows a similar XRD pattern, but the diffraction intensity is reduced, indicating that the crystalline nature was affected due to the V doping. With the increase in V content, the diffraction intensity gradually decreases, indicating that the weakening of crystallinity is caused by V and is closely related to the content of V. The crystallinity of the catalysts is NFO (93.9%), NFO-V0.1 (91.6%), NFO-V0.3 (59.2%), and NFO-V0.5 (49.3%), respectively. The XRD pattern of NFO-V0.3-P shows that the partial phosphating of the surface does not significantly change the original crystal structure of the catalyst. The new diffraction peaks with low intensity at 35.15°, 39.15°, and 48.07° correspond to (112), (211), and (220) crystal planes of NiP, respectively, which indicate that NiP appeared after phosphating.

TEM and HRTEM images provide more details on the changes in the catalyst structure. Figure 2(c) shows the polycrystalline structure of NFO, consisting of irregular nanoparticles with a particle size of 10 nm. The lattice fringes corresponding to NiFe2O4 on the (220), (311), (440), and (400) planes are observed in Figure 2(f), which verifies the above-mentioned XRD characterization. As shown in the TEM image of NFO-V0.3 (Figure 2d), the polycrystalline structure still exists, but the nanoparticle size is significantly reduced. The corresponding HRTEM (Figure 2g) shows a sizeable blurred area without visible lattice fringes, recognized as the amorphous phase, which shows that the introduction of V in the catalyst weakens the crystallization ability of NFO-V0.3. The introduction of a small amount of V causes part of Fe to be replaced by V. Due to the differences in atomic radius and electronic structure of V and Fe, the presence of V in the crystal lattice hinders the crystallization process, thereby weakening the crystallization ability of the catalyst [24]. Thus, part of the crystalline phase is transformed into an amorphous phase. At the same time, the limited crystallization ability prevents the catalyst nanoparticles from growing large enough, resulting in the phenomenon of nanoparticle size reduction after V doping. With an appropriate amount of V doping, some regions in the catalyst are transformed into the amorphous phase, but the rest can still be crystallized normally. The amorphous/crystalline mixed heterophase is constructed by adjusting the amount of V doping. The amorphous/crystalline mixed heterophase structure in NFO-V0.3 provides many vacancies and interfacial defects, providing more reactive sites for catalytic reactions [30]. As shown in Figure 2(h), such an amorphous/crystalline heterophase structure is preserved after phosphating in NFO-V0.3-P. The lattice diffraction fringes correspond to the NiP (122) plane to support the XRD characterization.

XPS was used to further evaluate the surface chemical composition and valence state of the catalysts. As shown in Figure S6(a), the existence of the V 2p peak and P 2p peak can be observed in the XPS total spectra of the three catalysts, verifying the existence of V and P elements. On the high-resolution P 2p XPS spectrum of NFO-V0.3-P (Figure S6b), the doublet peak in the 127–131 eV region is ascribed to P-metal bonding [31]. The broad peak centered at 132.8 eV comes from the P–O bonding of phosphorus species exposed to air [32], which further proves the existence of metal phosphide on the catalyst surface.

For transition metal oxides, the e g occupancy of the transition metal ions at the active site is an essential descriptor of OER activity because the e g orbitals directly participate in σ bonding with surface oxygen [33]. A small e g occupancy will lead to strong oxygen binding force, and the intermediate cannot be effectively desorbed; a large e g occupancy will inhibit the activation of oxygen and weaken the binding force of the intermediate [34]. Previous studies have found that when the e g occupancy is around 1.2, an ideal balance will be reached, and the catalyst shows the optimal OER activity [35,36]. Since Ni2+ has a valence electron configuration of (t 2g6 e g2), it can be assumed that Ni2+ (e g = 2) is in a high-spin state and Ni3+ (e g = 1) is in a high-spin state. According to the ratio of Ni2+ and Ni3+, the e g occupy can be calculated [37]. As shown in Figure 3(a), with the introduction of V, a high oxidation state peak corresponding to Ni3+ appears at 856.28 eV, and the characteristic peak corresponding to Ni2+ is significantly reduced. According to the characteristic peak area Ni3+/Ni2+ = 1.23, the calculated e g occupancy is approximately 1.44. It is also observed in Figure 3(b) that the V 2p3/2 peak, which should be observed at 517.5 eV, appears at 517 eV. The lower valence is due to the acceptance of electrons from Ni. After growing the phosphide heterojunction, the corresponding binding energy of Ni 2p3/2 shifts positively from 855.08 to 855.38 eV, and the binding energy of the V 2p3/2 peak (Figure S3d) further decreases to 516.8 eV. The ratio of Ni3+/Ni2+ continues to increase, and the e g occupancy is calculated to be 1.26 by the ratio, which means the oxidation state of Ni is higher. The characteristic peak at 853.4 eV is attributed to Ni-P, which proves the existence of the NiP crystal phase on the catalyst surface [31].

Figure 3 XPS spectra of NFO, NFO-V0.3, NFO-V0.3-P in (a) Ni 2p, (b) Fe 2p, (c) O 1 s, and (d) V 2p region.
Figure 3

XPS spectra of NFO, NFO-V0.3, NFO-V0.3-P in (a) Ni 2p, (b) Fe 2p, (c) O 1 s, and (d) V 2p region.

In the Fe 2p spectra shown in Figure 3(c), the signal mainly consists of two peaks near 712.7 and 724.3 eV, which belong to Fe 2p3/2 and Fe 2p1/2, respectively [38]. The Fe3+ content in high valence state increases after V doping and decreases after phosphating, which means that the overall oxidation state of Fe increases first and then decreases. The heterojunction changes the internal electronic structure of the catalyst, and more electrons are transferred around Fe3+ to ensure the high oxidation state and low e g occupancy of Ni in the catalytic active site. On the high-resolution O 1s XPS spectrum (Figure 3d), the peak at 529.7 eV is attributed to O-metal bonding, the peak at 532.6 eV is related to the hydroxyl species of surface adsorbed water molecules, while the peak at 531.2 eV is attributed to a large number of defect sites with low oxygen coordination, namely, oxygen vacancies [39]. It is clearly observed that the peak area at 531.2 eV increases with V doping and phosphide heterojunction. It indicates that amorphous/crystalline mixed heterophase and phosphide heterojunction bring more defects to the catalyst and are more favorable for OER activity [30]. EPR spectroscopy (Figure S7) also demonstrated changes in oxygen vacancies, and the enhanced EPR signal intensity at g = 2.003 is attributed to the significant increase in oxygen vacancies [40].

3.2 OER performance of catalysts

The OER activity of the catalysts was evaluated in 1 M KOH solution using a three-electrode cell, and commercial RuO2 was used for comparison. Clearly, catalysts with different V contents showed different degrees of OER activity improvement over NFO (Figure S8). NFO-V0.3 exhibits the lowest overpotentials of 309 and 350 mV at current densities of 20 and 100 mA cm−2. The enhanced OER activity is related to the formation of amorphous/crystalline heterophase and the regulation of electronic structure induced by V in the catalyst. After constructing the surface heterojunction, the OER activity of NFO-V0.3-P was further enhanced. As shown in Figure 4(a), NFO-V0.3-P exhibits low overpotentials of 277 mV and 310 mV at current densities of 20 and 100 mA cm−2, far superior to commercial RuO2. The Tafel plots (Figure 4c) converted from LSV curves can evaluate the reaction kinetics of the catalysts. NFO-V0.3-P shows the lowest Tafel slope of 45 mV dec−1 among all samples, outperforming NFO (77 mV dec−1), NFO-V0.3 (54 mV dec−1), and commercial RuO2 (62 mV dec−1). This indicates that the OER reaction kinetics of the catalyst are optimized by V doping and phosphide heterojunction.

Figure 4 (a) iR-corrected LSV curves of NFO, NFO-V0.3, NFO-V0.3-P, and RuO2. (b) A comparison of the overpotential values at the current densities of 20 and 100 mA cm−2. (c) Corresponding Tafel plots of the polarization curves in (a). (d) Nyquist plots of NFO, NFO-V0.3, NFO-V0.3-P. (e) The electrochemical C dl of NFO, NFO-V0.3, and NFO-V0.3-P. (f) OER chronopotentiometry measurement of NFO-V0.3-P catalyst at the current densities of 20 and 100 mA cm−2.
Figure 4

(a) iR-corrected LSV curves of NFO, NFO-V0.3, NFO-V0.3-P, and RuO2. (b) A comparison of the overpotential values at the current densities of 20 and 100 mA cm−2. (c) Corresponding Tafel plots of the polarization curves in (a). (d) Nyquist plots of NFO, NFO-V0.3, NFO-V0.3-P. (e) The electrochemical C dl of NFO, NFO-V0.3, and NFO-V0.3-P. (f) OER chronopotentiometry measurement of NFO-V0.3-P catalyst at the current densities of 20 and 100 mA cm−2.

As shown in Figure S9, the intrinsic catalytic activity of the catalysts can be compared by measuring the C dl in the potential range from 0.83 to 1.03 V to estimate the ECSA. NFO-V0.3 possesses the highest C dl (0.3 mF cm−2), attributed to more defects in the amorphous/crystalline phases, exposing the most reactive sites. Although part of the active surface area of NFO-V0.3-P is covered by the phosphide heterojunction, the conductivity and more oxygen vacancy defects brought by phosphating significantly increase the OER activity. The charge transport properties of the catalysts can be further explored through the EIS tests. Figure 4(d) shows that NFO-V0.3-P has the lowest R ct, verifying the enhanced overall conductivity by phosphide heterojunction. Although the amorphous phase can provide many reactive sites, the electrical conductivity of both the spinel phase and the amorphous phase is relatively poor. Therefore, the phosphide heterojunction in NFO-V0.3-P sacrifices little reactive surface area to significantly improve the overall conductivity of the catalyst, which is helpful to further improve the electrocatalytic activity.

In our designed strategies, the enhanced OER activity of the catalyst is achieved by tuning the crystal structure and electronic structure. The amorphous phase induced by V doping in the crystal structure can provide more reactive sites, and its poor conductivity is improved by the phosphide heterojunction. The V and P heteroatoms introduced by the V-doping and NiP heterojunction strategies, respectively, jointly promote electronic rearrangement. The transfer of electrons from Ni to V or other atoms achieves a higher valence state of Ni and an e g occupancy closer to 1.2, as well as lower binding energy of the catalyst for oxygen intermediates. The optimization of the catalyst's electronic structure benefits from the synergistic regulation of the two designed strategies. Therefore, the OER activity of the catalyst is greatly enhanced after adjusting various factors such as active sites, conductivity, and e g occupancy. Finally, we evaluated the stability and durability of the synthesized catalysts in an alkaline electrolyte by measuring chronopotentiometry curves at 20 and 100 mA cm−2 in alkaline media, which is a critical factor for the large-scale application of catalysts in industrial applications. Chronopotentiometry curves of NFO-V0.3-P in 1 M KOH (Figure 4f) show that the overpotential increased by only 4 mV after continuous electrolysis for 12 h, indicating good stability at both low and high current densities.

4 Conclusion

In conclusion, we successfully constructed amorphous/crystalline heterophase coupled with phosphide heterojunction in NFO-V0.3-P by V doping and surface phosphating. The phosphide heterojunction improves the poor conductivity caused by the amorphous phase and achieves an e g occupancy of 1.26 for Ni. As a result, the catalyst exhibits a low overpotential of 277 mV at 20 mA cm−2, a Tafel slope of 45 mV dec−1, and long-term stability in alkaline electrolytes. The amorphous/crystalline heterophase and heterojunction provide more active sites and higher conductivity and promote the electronic regulation of active sites. This work provides an instructive strategy to construct amorphous/crystalline heterophase coupled with heterojunction for synergistically enhanced OER performance.

  1. Funding information: The work was supported by the National Natural Science Foundation of China (No. 52002338), the Science and Technology Planning Project of Sichuan Province (No. 2021ZYD0053), and Key R&D Program of Sichuan Province (2022YFSY0024).

  2. Author contributions: All authors have accepted responsibility for the entire content of this manuscript and approved its submission.

  3. Conflict of interest: The authors state no conflict of interest.

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Received: 2022-04-25
Revised: 2022-05-15
Accepted: 2022-05-15
Published Online: 2022-11-25

© 2022 the author(s), published by De Gruyter

This work is licensed under the Creative Commons Attribution 4.0 International License.

Artikel in diesem Heft

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  3. Mechanical, morphological, and fracture-deformation behavior of MWCNTs-reinforced (Al–Cu–Mg–T351) alloy cast nanocomposites fabricated by optimized mechanical milling and powder metallurgy techniques
  4. Flammability and physical stability of sugar palm crystalline nanocellulose reinforced thermoplastic sugar palm starch/poly(lactic acid) blend bionanocomposites
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  6. Relationship between mechano-bactericidal activity and nanoblades density on chemically strengthened glass
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  18. Effect of plasticizers on the properties of sugar palm nanocellulose/cinnamon essential oil reinforced starch bionanocomposite films
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https://doi.org/10.1515/ntrev-2022-0450
Schlagwörter für diesen Artikel
spinel oxide; OER; electrocatalyst; doping; heterojunction; heterophase
Creative Commons
BY 4.0

Artikel in diesem Heft

  1. Research Articles
  2. Theoretical and experimental investigation of MWCNT dispersion effect on the elastic modulus of flexible PDMS/MWCNT nanocomposites
  3. Mechanical, morphological, and fracture-deformation behavior of MWCNTs-reinforced (Al–Cu–Mg–T351) alloy cast nanocomposites fabricated by optimized mechanical milling and powder metallurgy techniques
  4. Flammability and physical stability of sugar palm crystalline nanocellulose reinforced thermoplastic sugar palm starch/poly(lactic acid) blend bionanocomposites
  5. Glutathione-loaded non-ionic surfactant niosomes: A new approach to improve oral bioavailability and hepatoprotective efficacy of glutathione
  6. Relationship between mechano-bactericidal activity and nanoblades density on chemically strengthened glass
  7. In situ regulation of microstructure and microwave-absorbing properties of FeSiAl through HNO3 oxidation
  8. Research on a mechanical model of magnetorheological fluid different diameter particles
  9. Nanomechanical and dynamic mechanical properties of rubber–wood–plastic composites
  10. Investigative properties of CeO2 doped with niobium: A combined characterization and DFT studies
  11. Miniaturized peptidomimetics and nano-vesiculation in endothelin types through probable nano-disk formation and structure property relationships of endothelins’ fragments
  12. N/S co-doped CoSe/C nanocubes as anode materials for Li-ion batteries
  13. Synergistic effects of halloysite nanotubes with metal and phosphorus additives on the optimal design of eco-friendly sandwich panels with maximum flame resistance and minimum weight
  14. Octreotide-conjugated silver nanoparticles for active targeting of somatostatin receptors and their application in a nebulized rat model
  15. Controllable morphology of Bi2S3 nanostructures formed via hydrothermal vulcanization of Bi2O3 thin-film layer and their photoelectrocatalytic performances
  16. Development of (−)-epigallocatechin-3-gallate-loaded folate receptor-targeted nanoparticles for prostate cancer treatment
  17. Enhancement of the mechanical properties of HDPE mineral nanocomposites by filler particles modulation of the matrix plastic/elastic behavior
  18. Effect of plasticizers on the properties of sugar palm nanocellulose/cinnamon essential oil reinforced starch bionanocomposite films
  19. Optimization of nano coating to reduce the thermal deformation of ball screws
  20. Preparation of efficient piezoelectric PVDF–HFP/Ni composite films by high electric field poling
  21. MHD dissipative Casson nanofluid liquid film flow due to an unsteady stretching sheet with radiation influence and slip velocity phenomenon
  22. Effects of nano-SiO2 modification on rubberised mortar and concrete with recycled coarse aggregates
  23. Mechanical and microscopic properties of fiber-reinforced coal gangue-based geopolymer concrete
  24. Effect of morphology and size on the thermodynamic stability of cerium oxide nanoparticles: Experiment and molecular dynamics calculation
  25. Mechanical performance of a CFRP composite reinforced via gelatin-CNTs: A study on fiber interfacial enhancement and matrix enhancement
  26. A practical review over surface modification, nanopatterns, emerging materials, drug delivery systems, and their biophysiochemical properties for dental implants: Recent progresses and advances
  27. HTR: An ultra-high speed algorithm for cage recognition of clathrate hydrates
  28. Effects of microalloying elements added by in situ synthesis on the microstructure of WCu composites
  29. A highly sensitive nanobiosensor based on aptamer-conjugated graphene-decorated rhodium nanoparticles for detection of HER2-positive circulating tumor cells
  30. Progressive collapse performance of shear strengthened RC frames by nano CFRP
  31. Core–shell heterostructured composites of carbon nanotubes and imine-linked hyperbranched polymers as metal-free Li-ion anodes
  32. A Galerkin strategy for tri-hybridized mixture in ethylene glycol comprising variable diffusion and thermal conductivity using non-Fourier’s theory
  33. Simple models for tensile modulus of shape memory polymer nanocomposites at ambient temperature
  34. Preparation and morphological studies of tin sulfide nanoparticles and use as efficient photocatalysts for the degradation of rhodamine B and phenol
  35. Polyethyleneimine-impregnated activated carbon nanofiber composited graphene-derived rice husk char for efficient post-combustion CO2 capture
  36. Electrospun nanofibers of Co3O4 nanocrystals encapsulated in cyclized-polyacrylonitrile for lithium storage
  37. Pitting corrosion induced on high-strength high carbon steel wire in high alkaline deaerated chloride electrolyte
  38. Formulation of polymeric nanoparticles loaded sorafenib; evaluation of cytotoxicity, molecular evaluation, and gene expression studies in lung and breast cancer cell lines
  39. Engineered nanocomposites in asphalt binders
  40. Influence of loading voltage, domain ratio, and additional load on the actuation of dielectric elastomer
  41. Thermally induced hex-graphene transitions in 2D carbon crystals
  42. The surface modification effect on the interfacial properties of glass fiber-reinforced epoxy: A molecular dynamics study
  43. Molecular dynamics study of deformation mechanism of interfacial microzone of Cu/Al2Cu/Al composites under tension
  44. Nanocolloid simulators of luminescent solar concentrator photovoltaic windows
  45. Compressive strength and anti-chloride ion penetration assessment of geopolymer mortar merging PVA fiber and nano-SiO2 using RBF–BP composite neural network
  46. Effect of 3-mercapto-1-propane sulfonate sulfonic acid and polyvinylpyrrolidone on the growth of cobalt pillar by electrodeposition
  47. Dynamics of convective slippery constraints on hybrid radiative Sutterby nanofluid flow by Galerkin finite element simulation
  48. Preparation of vanadium by the magnesiothermic self-propagating reduction and process control
  49. Microstructure-dependent photoelectrocatalytic activity of heterogeneous ZnO–ZnS nanosheets
  50. Cytotoxic and pro-inflammatory effects of molybdenum and tungsten disulphide on human bronchial cells
  51. Improving recycled aggregate concrete by compression casting and nano-silica
  52. Chemically reactive Maxwell nanoliquid flow by a stretching surface in the frames of Newtonian heating, nonlinear convection and radiative flux: Nanopolymer flow processing simulation
  53. Nonlinear dynamic and crack behaviors of carbon nanotubes-reinforced composites with various geometries
  54. Biosynthesis of copper oxide nanoparticles and its therapeutic efficacy against colon cancer
  55. Synthesis and characterization of smart stimuli-responsive herbal drug-encapsulated nanoniosome particles for efficient treatment of breast cancer
  56. Homotopic simulation for heat transport phenomenon of the Burgers nanofluids flow over a stretching cylinder with thermal convective and zero mass flux conditions
  57. Incorporation of copper and strontium ions in TiO2 nanotubes via dopamine to enhance hemocompatibility and cytocompatibility
  58. Mechanical, thermal, and barrier properties of starch films incorporated with chitosan nanoparticles
  59. Mechanical properties and microstructure of nano-strengthened recycled aggregate concrete
  60. Glucose-responsive nanogels efficiently maintain the stability and activity of therapeutic enzymes
  61. Tunning matrix rheology and mechanical performance of ultra-high performance concrete using cellulose nanofibers
  62. Flexible MXene/copper/cellulose nanofiber heat spreader films with enhanced thermal conductivity
  63. Promoted charge separation and specific surface area via interlacing of N-doped titanium dioxide nanotubes on carbon nitride nanosheets for photocatalytic degradation of Rhodamine B
  64. Elucidating the role of silicon dioxide and titanium dioxide nanoparticles in mitigating the disease of the eggplant caused by Phomopsis vexans, Ralstonia solanacearum, and root-knot nematode Meloidogyne incognita
  65. An implication of magnetic dipole in Carreau Yasuda liquid influenced by engine oil using ternary hybrid nanomaterial
  66. Robust synthesis of a composite phase of copper vanadium oxide with enhanced performance for durable aqueous Zn-ion batteries
  67. Tunning self-assembled phases of bovine serum albumin via hydrothermal process to synthesize novel functional hydrogel for skin protection against UVB
  68. A comparative experimental study on damping properties of epoxy nanocomposite beams reinforced with carbon nanotubes and graphene nanoplatelets
  69. Lightweight and hydrophobic Ni/GO/PVA composite aerogels for ultrahigh performance electromagnetic interference shielding
  70. Research on the auxetic behavior and mechanical properties of periodically rotating graphene nanostructures
  71. Repairing performances of novel cement mortar modified with graphene oxide and polyacrylate polymer
  72. Closed-loop recycling and fabrication of hydrophilic CNT films with high performance
  73. Design of thin-film configuration of SnO2–Ag2O composites for NO2 gas-sensing applications
  74. Study on stress distribution of SiC/Al composites based on microstructure models with microns and nanoparticles
  75. PVDF green nanofibers as potential carriers for improving self-healing and mechanical properties of carbon fiber/epoxy prepregs
  76. Osteogenesis capability of three-dimensionally printed poly(lactic acid)-halloysite nanotube scaffolds containing strontium ranelate
  77. Silver nanoparticles induce mitochondria-dependent apoptosis and late non-canonical autophagy in HT-29 colon cancer cells
  78. Preparation and bonding mechanisms of polymer/metal hybrid composite by nano molding technology
  79. Damage self-sensing and strain monitoring of glass-reinforced epoxy composite impregnated with graphene nanoplatelet and multiwalled carbon nanotubes
  80. Thermal analysis characterisation of solar-powered ship using Oldroyd hybrid nanofluids in parabolic trough solar collector: An optimal thermal application
  81. Pyrene-functionalized halloysite nanotubes for simultaneously detecting and separating Hg(ii) in aqueous media: A comprehensive comparison on interparticle and intraparticle excimers
  82. Fabrication of self-assembly CNT flexible film and its piezoresistive sensing behaviors
  83. Thermal valuation and entropy inspection of second-grade nanoscale fluid flow over a stretching surface by applying Koo–Kleinstreuer–Li relation
  84. Mechanical properties and microstructure of nano-SiO2 and basalt-fiber-reinforced recycled aggregate concrete
  85. Characterization and tribology performance of polyaniline-coated nanodiamond lubricant additives
  86. Combined impact of Marangoni convection and thermophoretic particle deposition on chemically reactive transport of nanofluid flow over a stretching surface
  87. Spark plasma extrusion of binder free hydroxyapatite powder
  88. An investigation on thermo-mechanical performance of graphene-oxide-reinforced shape memory polymer
  89. Effect of nanoadditives on the novel leather fiber/recycled poly(ethylene-vinyl-acetate) polymer composites for multifunctional applications: Fabrication, characterizations, and multiobjective optimization using central composite design
  90. Design selection for a hemispherical dimple core sandwich panel using hybrid multi-criteria decision-making methods
  91. Improving tensile strength and impact toughness of plasticized poly(lactic acid) biocomposites by incorporating nanofibrillated cellulose
  92. Green synthesis of spinel copper ferrite (CuFe2O4) nanoparticles and their toxicity
  93. The effect of TaC and NbC hybrid and mono-nanoparticles on AA2024 nanocomposites: Microstructure, strengthening, and artificial aging
  94. Excited-state geometry relaxation of pyrene-modified cellulose nanocrystals under UV-light excitation for detecting Fe3+
  95. Effect of CNTs and MEA on the creep of face-slab concrete at an early age
  96. Effect of deformation conditions on compression phase transformation of AZ31
  97. Application of MXene as a new generation of highly conductive coating materials for electromembrane-surrounded solid-phase microextraction
  98. A comparative study of the elasto-plastic properties for ceramic nanocomposites filled by graphene or graphene oxide nanoplates
  99. Encapsulation strategies for improving the biological behavior of CdS@ZIF-8 nanocomposites
  100. Biosynthesis of ZnO NPs from pumpkin seeds’ extract and elucidation of its anticancer potential against breast cancer
  101. Preliminary trials of the gold nanoparticles conjugated chrysin: An assessment of anti-oxidant, anti-microbial, and in vitro cytotoxic activities of a nanoformulated flavonoid
  102. Effect of micron-scale pores increased by nano-SiO2 sol modification on the strength of cement mortar
  103. Fractional simulations for thermal flow of hybrid nanofluid with aluminum oxide and titanium oxide nanoparticles with water and blood base fluids
  104. The effect of graphene nano-powder on the viscosity of water: An experimental study and artificial neural network modeling
  105. Development of a novel heat- and shear-resistant nano-silica gelling agent
  106. Characterization, biocompatibility and in vivo of nominal MnO2-containing wollastonite glass-ceramic
  107. Entropy production simulation of second-grade magnetic nanomaterials flowing across an expanding surface with viscidness dissipative flux
  108. Enhancement in structural, morphological, and optical properties of copper oxide for optoelectronic device applications
  109. Aptamer-functionalized chitosan-coated gold nanoparticle complex as a suitable targeted drug carrier for improved breast cancer treatment
  110. Performance and overall evaluation of nano-alumina-modified asphalt mixture
  111. Analysis of pure nanofluid (GO/engine oil) and hybrid nanofluid (GO–Fe3O4/engine oil): Novel thermal and magnetic features
  112. Synthesis of Ag@AgCl modified anatase/rutile/brookite mixed phase TiO2 and their photocatalytic property
  113. Mechanisms and influential variables on the abrasion resistance hydraulic concrete
  114. Synergistic reinforcement mechanism of basalt fiber/cellulose nanocrystals/polypropylene composites
  115. Achieving excellent oxidation resistance and mechanical properties of TiB2–B4C/carbon aerogel composites by quick-gelation and mechanical mixing
  116. Microwave-assisted sol–gel template-free synthesis and characterization of silica nanoparticles obtained from South African coal fly ash
  117. Pulsed laser-assisted synthesis of nano nickel(ii) oxide-anchored graphitic carbon nitride: Characterizations and their potential antibacterial/anti-biofilm applications
  118. Effects of nano-ZrSi2 on thermal stability of phenolic resin and thermal reusability of quartz–phenolic composites
  119. Benzaldehyde derivatives on tin electroplating as corrosion resistance for fabricating copper circuit
  120. Mechanical and heat transfer properties of 4D-printed shape memory graphene oxide/epoxy acrylate composites
  121. Coupling the vanadium-induced amorphous/crystalline NiFe2O4 with phosphide heterojunction toward active oxygen evolution reaction catalysts
  122. Graphene-oxide-reinforced cement composites mechanical and microstructural characteristics at elevated temperatures
  123. Gray correlation analysis of factors influencing compressive strength and durability of nano-SiO2 and PVA fiber reinforced geopolymer mortar
  124. Preparation of layered gradient Cu–Cr–Ti alloy with excellent mechanical properties, thermal stability, and electrical conductivity
  125. Recovery of Cr from chrome-containing leather wastes to develop aluminum-based composite material along with Al2O3 ceramic particles: An ingenious approach
  126. Mechanisms of the improved stiffness of flexible polymers under impact loading
  127. Anticancer potential of gold nanoparticles (AuNPs) using a battery of in vitro tests
  128. Review Articles
  129. Proposed approaches for coronaviruses elimination from wastewater: Membrane techniques and nanotechnology solutions
  130. Application of Pickering emulsion in oil drilling and production
  131. The contribution of microfluidics to the fight against tuberculosis
  132. Graphene-based biosensors for disease theranostics: Development, applications, and recent advancements
  133. Synthesis and encapsulation of iron oxide nanorods for application in magnetic hyperthermia and photothermal therapy
  134. Contemporary nano-architectured drugs and leads for ανβ3 integrin-based chemotherapy: Rationale and retrospect
  135. State-of-the-art review of fabrication, application, and mechanical properties of functionally graded porous nanocomposite materials
  136. Insights on magnetic spinel ferrites for targeted drug delivery and hyperthermia applications
  137. A review on heterogeneous oxidation of acetaminophen based on micro and nanoparticles catalyzed by different activators
  138. Early diagnosis of lung cancer using magnetic nanoparticles-integrated systems
  139. Advances in ZnO: Manipulation of defects for enhancing their technological potentials
  140. Efficacious nanomedicine track toward combating COVID-19
  141. A review of the design, processes, and properties of Mg-based composites
  142. Green synthesis of nanoparticles for varied applications: Green renewable resources and energy-efficient synthetic routes
  143. Two-dimensional nanomaterial-based polymer composites: Fundamentals and applications
  144. Recent progress and challenges in plasmonic nanomaterials
  145. Apoptotic cell-derived micro/nanosized extracellular vesicles in tissue regeneration
  146. Electronic noses based on metal oxide nanowires: A review
  147. Framework materials for supercapacitors
  148. An overview on the reproductive toxicity of graphene derivatives: Highlighting the importance
  149. Antibacterial nanomaterials: Upcoming hope to overcome antibiotic resistance crisis
  150. Research progress of carbon materials in the field of three-dimensional printing polymer nanocomposites
  151. A review of atomic layer deposition modelling and simulation methodologies: Density functional theory and molecular dynamics
  152. Recent advances in the preparation of PVDF-based piezoelectric materials
  153. Recent developments in tensile properties of friction welding of carbon fiber-reinforced composite: A review
  154. Comprehensive review of the properties of fly ash-based geopolymer with additive of nano-SiO2
  155. Perspectives in biopolymer/graphene-based composite application: Advances, challenges, and recommendations
  156. Graphene-based nanocomposite using new modeling molecular dynamic simulations for proposed neutralizing mechanism and real-time sensing of COVID-19
  157. Nanotechnology application on bamboo materials: A review
  158. Recent developments and future perspectives of biorenewable nanocomposites for advanced applications
  159. Nanostructured lipid carrier system: A compendium of their formulation development approaches, optimization strategies by quality by design, and recent applications in drug delivery
  160. 3D printing customized design of human bone tissue implant and its application
  161. Design, preparation, and functionalization of nanobiomaterials for enhanced efficacy in current and future biomedical applications
  162. A brief review of nanoparticles-doped PEDOT:PSS nanocomposite for OLED and OPV
  163. Nanotechnology interventions as a putative tool for the treatment of dental afflictions
  164. Recent advancements in metal–organic frameworks integrating quantum dots (QDs@MOF) and their potential applications
  165. A focused review of short electrospun nanofiber preparation techniques for composite reinforcement
  166. Microstructural characteristics and nano-modification of interfacial transition zone in concrete: A review
  167. Latest developments in the upconversion nanotechnology for the rapid detection of food safety: A review
  168. Strategic applications of nano-fertilizers for sustainable agriculture: Benefits and bottlenecks
  169. Molecular dynamics application of cocrystal energetic materials: A review
  170. Synthesis and application of nanometer hydroxyapatite in biomedicine
  171. Cutting-edge development in waste-recycled nanomaterials for energy storage and conversion applications
  172. Biological applications of ternary quantum dots: A review
  173. Nanotherapeutics for hydrogen sulfide-involved treatment: An emerging approach for cancer therapy
  174. Application of antibacterial nanoparticles in orthodontic materials
  175. Effect of natural-based biological hydrogels combined with growth factors on skin wound healing
  176. Nanozymes – A route to overcome microbial resistance: A viewpoint
  177. Recent developments and applications of smart nanoparticles in biomedicine
  178. Contemporary review on carbon nanotube (CNT) composites and their impact on multifarious applications
  179. Interfacial interactions and reinforcing mechanisms of cellulose and chitin nanomaterials and starch derivatives for cement and concrete strength and durability enhancement: A review
  180. Diamond-like carbon films for tribological modification of rubber
  181. Layered double hydroxides (LDHs) modified cement-based materials: A systematic review
  182. Recent research progress and advanced applications of silica/polymer nanocomposites
  183. Modeling of supramolecular biopolymers: Leading the in silico revolution of tissue engineering and nanomedicine
  184. Recent advances in perovskites-based optoelectronics
  185. Biogenic synthesis of palladium nanoparticles: New production methods and applications
  186. A comprehensive review of nanofluids with fractional derivatives: Modeling and application
  187. Electrospinning of marine polysaccharides: Processing and chemical aspects, challenges, and future prospects
  188. Electrohydrodynamic printing for demanding devices: A review of processing and applications
  189. Rapid Communications
  190. Structural material with designed thermal twist for a simple actuation
  191. Recent advances in photothermal materials for solar-driven crude oil adsorption
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Heruntergeladen am 6.9.2025 von https://www.degruyterbrill.com/document/doi/10.1515/ntrev-2022-0450/html?lang=de
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