3D Porous Materials Research Articles

Numerical model of jet formation during melt electrowriting for fabrication of precise structures

Melt electrowriting (MEW) is an innovative technique for fabricating 3D porous materials or scaffolds with microscale architectures. However, the multitude of printing parameters makes precise control over the placement of microscale polymer fibers challenging. This study presents a new strategy for creating complex 3D structures using multiparametric MEW technology, which enhances printing accuracy with minimal human intervention. We developed and validated a numerical model to simulate jet formation and predict the critical translational speed (CTS). This model can precisely identify the effects of numerous printing parameters and improve printing efficiency and accuracy while reducing costs, thus facilitating precise MEW deposition. Using this approach, we manufactured soft, stretchable constructs with a high surface area optimized through fine-tuned printing parameters. This straightforward and efficient technology enables the design of high-sensitivity strain sensors for monitoring human motion and stretchable devices for circuit protection. Furthermore, we examined the effect of printing accuracy and fiber orientation on cellular organization. Immunochemical staining demonstrated that aligned and high-precision scaffolds promote oriented growth. Additionally, the curved MEW structures open new avenues for exploring the combined effects of topographical cues and mechanical stimulation on nerve cell behaviors. This printing strategy provides valuable insights for future research on complex patterns using MEW for flexible electronics and tissue engineering.

Emulsion-Templated Gelatin/Amino Acids/Chitosan Macroporous Hydrogels with Adjustable Internal Dimensions for Three-Dimensional Stem Cell Culture.

The demand for macroporous hydrogel scaffolds with interconnected porous and open-pore structures is crucial for advancing research and development in cell culture and tissue regeneration. Existing techniques for creating 3D porous materials and controlling their porosity are currently constrained. This study introduces a novel approach for producing highly interconnected aspartic acid-gelatin macroporous hydrogels (MHs) with precisely defined open pore structures using a one-step emulsification polymerization method with surface-modified silica nanoparticles as Pickering stabilizers. Macroporous hydrogels offer adjustable pore size and pore throat size within the ranges of 50 to 130 μm and 15 to 27 μm, respectively, achieved through variations in oil-in-water ratio and solid content. The pore wall thickness of the macroporous hydrogel can be as thin as 3.37 μm and as thick as 6.7 μm. In addition, the storage modulus of the macroporous hydrogels can be as high as 7250 Pa, and it maintains an intact rate of more than 92% after being soaked in PBS for 60 days, which is also good performance for use as a biomedical scaffold material. These hydrogels supported the proliferation of human dental pulp stem cells (hDPSCs) over a 30 day incubation period, stretching the cell morphology and demonstrating excellent biocompatibility and cell adhesion. The combination of these desirable attributes makes them highly promising for applications in stem cell culture and tissue regeneration, underscoring their potential significance in advancing these fields.

In situ loading of ZnO on hierarchical porous carbon derived from banana-peel waste to enrich mechanism for microwave absorption

Biomass has received widespread attention due to its easy availability, low cost, and environmental friendliness as an electromagnetic wave absorber candidate. Inspired by the natural porosity of biomass, the three-dimensional (3D) porous carbon materials derived from banana peels were prepared via coordination and pyrolysis carbonization. A conductive network of biomass-zinc complexes was constructed by introducing Zn2+ to coordinate with organic polymers. Hierarchical porous carbon/ZnO composites with a 3D skeleton network were obtained, which demonstrated outstanding electromagnetic wave absorption performance with an effective absorption bandwidth (EAB) of 6.72 GHz and the reflection loss (RL) of −44.18 dB. The banana peel-derived porous carbon (BPC) embedded with ZnO particles brings about conductive loss and interface polarization, further enriching the microwave loss mechanisms. This work offers a fresh idea for creating a green, sustainable, and high-value functional carbon-based composite material.

Investigation of synergistic effects incorporating esterified lignin and guar gum composite aerogel for sustained oil spill cleanup

The recently developed aerogel demonstrates a high capacity for pollutant absorption, making it an environmentally friendly option for oily water treatment. In an effort to reduce the adverse effects of the black liquor accumulation in the pulp industry, this study focused on utilizing the mentioned abundant bio-resource lignin, which can be applied to various high-value applications such as 3D porous materials for oil spill cleanup. Lignin, precipitated from the black liquor, was esterified using maleic anhydride as the esterifying reagent to enhance the hydrophobicity. Then, the composite aerogel fabricated from esterified lignin and guar gum (GG) was successfully prepared through the facile freeze-drying, using glutaraldehyde (GA) as the cross-linker. The resulting aerogel exhibited high porosity values exceeding 95%, low density (27.4 mg/cm3), and an impressive absorption capacity of 32.5 g/g for sunflower oil. These results demonstrate the potential of black liquor utilization as a bio-waste source of lignin and highlight the cost-effective guar gum-esterified lignin composite aerogel, which exhibits remarkable oil absorption capabilities and environmental sustainability promotion.

Cathode|Electrolyte Interface Engineering by a Hydrogel Polymer Electrolyte for a 3D Porous High-Voltage Cathode Material in a Quasi-Solid-State Zinc Metal Battery by In Situ Polymerization.

This work highlights the development of a superior cathode|electrolyte interface for the quasi solid-state rechargeable zinc metal battery (QSS-RZMB) by a novel hydrogel polymer electrolyte using an ultraviolet (UV) light-assisted in situ polymerization strategy. By integrating the cathode with a thin layer of the hydrogel polymer electrolyte, this technique produces an integrated interface that ensures quick Zn2+ ion conduction. The coexistence of nanowires for direct electron routes and the enhanced electrolyte ion infiltration and diffusion by the 3D porous flower structure with a wide open surface of the Zn-MnO electrode complements the interface formation during the in situ polymerization process. The QSS-RZMB configured with an integrated cathode (i-Zn-MnO) and the hydrogel polymer electrolyte (PHPZ-30) as the separator yields a comparable specific energy density of 214.14Whkg-1 with that of its liquid counterpart (240.38Whkg-1, 0.5MZn(CF3SO3)2 aqueous electrolyte). Other noteworthy features of the presented QSS-RZMB system include its superior cycle life of over 1000 charge-discharge cycles and 85% capacity retention with 99% coulombic efficiency at the current density of 1.0Ag-1, compared to only 60% capacity retention over 500 charge-discharge cycles displayed by the liquid-state system under the same operating conditions.

Combining the micromechanical approach and boundary element method for estimating the effective permeability of 2D porous materials with arbitrarily shaped pores

Combining the micromechanical approach and boundary element method for estimating the effective permeability of 2D porous materials with arbitrarily shaped pores

Boron-manganese-nitrogen co-doped three-dimensional porous carbon realizes superior capacitive lithium-ion storage

Three-dimensional (3D) porous carbon has sufficient specific surface area and anchor positioning points. The pore structure facilitates uniform charge distribution, and buffers volume changes during stripping. However, single carbon materials have limited theoretical capacity and short cycle life. Here, 3D porous carbon material BCN/Mn-6 (B,N and Mn co-doped porous carbon with 6 mmol Mn content) co-doped with manganese, boron and nitrogen was synthesized by heat treatment. Affective modulation of the material structure and surface functional groups was achieved by adjusting the amount of manganese doping. The metal element doping can promote the diffusion of lithium ions, and the formed vacancies and defects can be used as lithium storage sites. Nitrogen doping can improve the dispersion and stability of metals and oxides, and regulate the redox capacity. Co-doping of metals and heteroatoms synergistically improves electrical conductivity. Thus, BCN/Mn-6 exhibits excellent cycling stability (99.60 % Coulombic efficiency after 300 cycles) and specific capacity (779.9 mAh/g), and shows capacity rise. This study provides a new direction for the preparation of carbon-based electrode materials doped with heteroatoms and the study of capacitive energy storage mechanisms.

Underoil superhydrophilic flame-retardant 3D porous composite for efficient on-demand emulsion separation: Interface engineering design on sphagnum moss

Oil pollution and the energy crisis make oil-water separation an urgent for human need. The widespread use of materials with a single emulsion separation capability is limited. Multifunctional on-demand separation materials can adapt to a wide range of application scenarios, thus having a wider range of applications. The underoil superhydrophilic surface is of great significance for realizing the on-demand separation of oil/water emulsions through the removal of water in the oil and oil in the water. A 3D porous emulsion separation material based on the superhydrophilic principle of sphagnum moss was designed. The material was prepared in a simple step by taking advantage of the adhesion of polydopamine and the introduction of the as-prepared superhydrophilic BaSO4 nanoparticles to achieve superhydrophilicity with a water contact angle (WCA) of 0° and an oil contact angle (OCA) of 157.3°, resulting in excellent separation performance for both water-in-oil and oil-in-water emulsions. Underoil superhydrophilic porous composite (OSPC) can complete two kinds of emulsion separations by filtration or adsorption. It adsorbs water from water-in-oil emulsion to achieve separation, with a good adsorption capacity of 74.38 g/g and efficiency up to 99%. It can also filter oil-in-water emulsions with an efficiency of 99.92%. The separation efficiencies are all almost unchanged after ten separation cycles. Furthermore, the material has excellent flame retardancy, which reduces the possibility of secondary disasters. The three-dimensional porous sponge has excellent on-demand separation performance for multiple emulsions. It provides a new preparation strategy for underoil superhydrophilic materials and a new idea for the design direction of special wetting materials for the on-demand separation of oil/water emulsions.

Maillard Reaction Inspired Microexplosion toward Fast Synthesis of Two-Dimensional Mesoporous Tin Oxides for Efficient Chemiresistive Gas Sensing.

Two-dimensional (2D) mesoporous transition metal oxides are highly desired in various applications, but their fast and low-cost synthesis remains a great challenge. Herein, a Maillard reaction inspired microexplosion approach is applied to rapidly synthesize ultrathin 2D mesoporous tin oxide (mSnO2). During the microexplosion between granular ammonia nitrate with melanoidin at high temperature, the organic species can be carbonized and expanded rapidly due to the instantaneous release of gases, thus producing ultrathin carbonaceous templates with rich functional groups to effectively anchor SnO2 nanoparticles on the surface. The subsequent removal of carbonaceous templates via calcination in air results in the formation of 2D mSnO2 due to the confinement effect of the templates. Pd nanoparticles are controllably deposited on the surface of 2D mSnO2 via in situ reduction, forming ultrathin 2D Pd/mSnO2 nanocomposites with thicknesses of 6-8 nm. Owing to the unique 2D mesoporous structure with rich oxygen defects and highly exposed metal-metal oxide interfaces, 2D Pd/mSnO2 exhibits excellent sensing performance toward acetone with high sensitivity, a short response time, and good selectivity under low working temperature (100 °C). This fast and convenient microexplosion synthesis strategy opens up the possibility of constructing 2D porous functional materials for various applications including high-performance gas sensors.

In Situ Laser-Induced 3D Porous Graphene within Transparent Polymers for Encapsulation-Free and Tunable Ultrabroadband Terahertz Absorption.

Three-dimensional (3D) porous carbon materials have great potential for fabricating flexible tunable broadband absorbers owing to their high electrical conductivity, strong dielectric loss, and unique microstructure. Herein, we introduce an innovative method for synthesizing 3D porous graphene that incorporates advanced tuning and encapsulation processes to augment its functional efficacy. Through the modulation of both thermal and nonthermal interactions between a femtosecond (fs) laser and a polydimethylsiloxane (PDMS) film, we have synergistically fine-tuned the surface morphology and lattice properties of 3D porous graphene. This approach enabled us to create a flexible terahertz (THz) absorber with customizable characteristics, boasting an impressive absorbance range of 80%-99% in the 0.4-1.0 THz spectrum, alongside a peak reflection loss (RL) of up to 35.6 dB. Furthermore, we have successfully demonstrated the production of photoinduced 3D porous graphene within a PDMS film, which serves as both a carbon precursor and protective layer. This simplifies the conventional packaging process. These devices exhibit a RL of up to 41.6 dB and an absorption bandwidth of 2.5 THz (0.6-3.1 THz). Our study presents a production methodology for high-performance, flexible THz absorbers, offering a straightforward and innovative solution for the rapid development of sophisticated, flexible THz absorbing materials.

Tunable 2D Conjugated Porous Organic Polymer Films for Precise Molecular Nanofiltration and Optoelectronics.

Structural design of 2D conjugated porous organic polymer films (2D CPOPs), by tuning linkage chemistries and pore sizes, provides great adaptability for various applications, including membrane separation. Here, four free-standing 2D CPOP films of imine- or hydrazone-linked polymers (ILP/HLP) in combination with benzene (B-ILP/HLP) and triphenylbenzene (TPB-ILP/HLP) aromatic cores are synthesized. The anisotropic disordered films, composed of polymeric layered structures, can be exfoliated into ultrathin 2D-nanosheets with layer-dependent electrical properties. The bulk CPOP films exhibit structure-dependent optical properties, triboelectric nanogenerator output, and robust mechanical properties, rivaling previously reported 2D polymers and porous materials. The exfoliation energies of the 2D CPOPs and their mechanical behavior at the molecular level are investigated using density function theory (DFT) and molecular dynamics (MD) simulations, respectively. Exploiting the structural tunability, the comparative organic solvent nanofiltration (OSN) performance of six membranes having different pore sizes and linkages to yield valuable trends in molecular weight selectivity is investigated. Interestingly, the OSN performances follow the predicted transport modeling values based on theoretical pore size calculations, signifying the existence of permanent porosity in these materials. The membranes exhibit excellent stability in organic solvents at high pressures devoid of any structural deformations, revealing their potential in practical OSN applications.

FeNi alloy embedded in three-dimensional nitrogen-doped porous carbon as bifunctional oxygen electrocatalysts for rechargeable Zn-air batteries

Iron‑nickel (FeNi) alloy is one of the efficient bifunctional oxygen electrocatalysts for zinc-air batteries (ZABs). However, FeNi alloy nanoparticles prepared by traditional synthesis strategies are easy to agglomerate and have non-uniform sizes, which is not conducive to the improvement of catalytic activity and stability. Here, we have successfully encapsulated two different kinds of nitrogen-rich metal phthalocyanines (MPcs) in situ doping in zeolitic imidazolate framework (ZIF-8) homogeneously by the “double solvents” method. The ligand nitrogen and macrocyclic structure of MPcs encapsulated in ZIF-8 not only helps metal dispersion and enhances the metal-ligand‑nitrogen (M-Nx) structure, but also enhances the graphitisation of three-dimensional (3D) porous carbon after pyrolysis. Thus, a FeNi alloy uniformly embedded in 3D nitrogen-doped porous carbon materials (FeNi@NC) was constructed in the subsequent pyrolysis process and used as an efficient bifunctional oxygen reduction/evolution (ORR/OER) electrocatalyst for rechargeable ZABs. Impressively, the FeNi@NC catalyst carries high half-wave potential (0.850 V) in ORR and the low overpotential (291 mV) in OER, significantly better than Pt/C (0.830 V) and RuO2 (307 mV), respectively. In addition, the rechargeable ZAB assembled with FeNi@NC air cathode has a specific capacity of 649 mW cm−2 and shows no significant degradation after 240 h of charging and discharging cycles. This study provides a new design idea for the manufacture of carbon-supported non-noble metal alloy catalysts with bifunctional oxygen catalytic activity, and verifies the feasibility of regulating the composition of non-noble metals to construct a rechargeable ZABs with excellent performance.

Confined cobalt single‐atom catalysts with strong electronic metal‐support interactions based on a biomimetic self‐assembly strategy

AbstractDesigning high‐performance and low‐cost electrocatalysts for oxygen evolution reaction (OER) is critical for the conversion and storage of sustainable energy technologies. Inspired by the biomineralization process, we utilized the phosphorylation sites of collagen molecules to combine with cobalt‐based mononuclear precursors at the molecular level and built a three‐dimensional (3D) porous hierarchical material through a bottom‐up biomimetic self‐assembly strategy to obtain single‐atom catalysts confined on carbonized biomimetic self‐assembled carriers (Co SACs/cBSC) after subsequent high‐temperature annealing. In this strategy, the biomolecule improved the anchoring efficiency of the metal precursor through precise functional groups; meanwhile, the binding‐then‐assembling strategy also effectively suppressed the nonspecific adsorption of metal ions, ultimately preventing atomic agglomeration and achieving strong electronic metal‐support interactions (EMSIs). Experimental characterizations confirm that binding forms between cobalt metal and carbonized self‐assembled substrate (Co–O4–P). Theoretical calculations disclose that the local environment changes significantly tailored the Co d‐band center, and optimized the binding energy of oxygenated intermediates and the energy barrier of oxygen release. As a result, the obtained Co SACs/cBSC catalyst can achieve remarkable OER activity and 24 h durability in 1 M KOH (η10 at 288 mV; Tafel slope of 44 mV dec−1), better than other transition metal‐based catalysts and commercial IrO2. Overall, we presented a self‐assembly strategy to prepare transition metal SACs with strong EMSIs, providing a new avenue for the preparation of efficient catalysts with fine atomic structures.

Dynamics of meniscus-bound particle clusters in extensional flow

Capillary suspensions are three-phase mixtures containing a solid particulate phase, a continuous liquid phase, and a second immiscible liquid forming capillary bridges between particles. Capillary suspensions are encountered in a wide array of applications including 3D printing, porous materials, and food formulations, but despite recent progress, the micromechanics of particle clusters in flow is not fully understood. In this work, we study the dynamics of meniscus-bound particle clusters in planar extensional flow using a Stokes trap, which is an automated flow control technique that allows for precise manipulation of freely suspended particles or particle clusters in flow. Focusing on the case of a two-particle doublet, we use a combination of experiments and analytical modeling to understand how particle clusters rearrange, deform, and ultimately break up in extensional flow. The time required for cluster breakup is quantified as a function of capillary number Ca and meniscus volume V. Importantly, a critical capillary number Cacrit for cluster breakup is determined using a combination of experiments and modeling. Cluster relaxation experiments are also performed by deforming particle clusters in flow, followed by flow cessation prior to breakup and observing cluster relaxation dynamics under zero-flow conditions. In all cases, experiments are complemented by an analytical model that accounts for capillary forces, lubrication forces, hydrodynamic drag forces, and hydrodynamic interactions acting on the particles. Results from the analytical models are found to be in good agreement with experiments. Overall, this work provides a new quantitative understanding of the deformation dynamics of capillary clusters in extensional flow.

Low-crystallinity conductive multivalence iron sulfide-embedded S-doped anode and high-surface area O-doped cathode of 3D porous N-rich graphitic carbon frameworks for high-performance sodium-ion hybrid energy storages

Sodium-ion hybrid energy storages (SIHESs) are promising electrochemical energy storages for many applications, but their low energy and power densities are yet to be overcome. Herein, we report a strategy to realize ultrahigh-energy density and fast-rechargeable SIHESs. Ultrafine iron sulfide-embedded S-doped carbon/graphene (FS/C/G) anode materials are synthesized from iron-based metal-organic framework (MOF)/graphene oxide heterostructures via graphitic carbon formation and sulfidation. Operando and ex-situ analyses reveal that cycled iron sulfides are rescaled into low-crystallinity conductive fragments with Fe vacancies and multivalence Fe2+/Fe3+ states. Size reduction to fragments inside a 3D porous S-doped N-rich graphitic carbon framework induces high-capacity/high-rate FS/C/G performance. Moreover, 3D porous O-doped carbon cathode materials are synthesized from zeolitic imidazolate frameworks (ZIFs) via pyrolysis-assisted micropore and KOH-assisted mesopore formations. This ZIF-derived porous carbon (ZDPC) has a ∼20-fold higher surface area (3972 m2/g) than conventional ZDCs, O-induced micropores/N-rich sites for high capacity, heteroatom-induced ion-accessible defects/mesopores, and N-rich conductive graphitic carbon networks. Additionally, FS/C/G//ZDPC SHHES benefits from diffusion-controlled and capacitive reactions, as demonstrated by its hitherto highest energy density of 247 Wh kg-1 outperforming state-of-the-art SIHESs, fast-rechargeable power density (up to 34,748 W kg-1) exceeding battery-type reactions by more than 100 folds, and cycle stability with ∼100 % Coulombic efficiency over 5000 charge-discharge cycles.

Green one-pot synthesis of spongy hierarchical porous carbon with interconnected channels towards high-performance supercapacitors

Green and convenient construction of three-dimensional (3D) hierarchical porous carbon for supercapacitors (SCs) has drawn widespread attention due to their effective ion adsorption and transport capabilities. In this study, sucrose-derived spongy hierarchical porous carbon materials were successfully prepared using a one-step carbonization process with sodium chloride and sodium bicarbonate acting as collaborative pore-forming agents. The optimal carbon material exhibits a distinct 3D spongy structure with interconnected channels, high specific surface area, and proper pore size distribution. Consequently, it displays a specific capacitance of 263.5 F g−1 at 0.5 A g−1 and could retain 221.9 F g−1 (84.21%) at 20 A g−1. Additionally, the as-fabricated device delivers a supreme energy density of 17.0 Wh kg−1 at 80 W kg−1 and possesses exceptional cycling stability of 94.36% after 20000 cycles. Through the combination of raw material carbonization properties and synergistic pore-making mechanisms, the present work provides an effective and eco-friendly approach for fabricating 3D spongy hierarchical porous carbon materials with interconnected channels for high-performance SCs.

Bio-carbon coil aerogels from tea waste: A sustainable solution for efficient oil-water separation

Discharging wastewater containing oils, fats, and organic solvents into water bodies poses a significant threat to the already limited freshwater resources. In recent years, three-dimensional (3D) porous adsorbent materials, such as aerogel materials, have gained attention for their high separation effectiveness in adsorption technology. However, the poor mechanical strength of existing aerogel materials limits their application in oil–water separation. To address this challenge, this study proposes to use carbon coils obtained from tea waste as a template for producing low-cost, ultra-light, elastic, and highly recyclable bio-carbon coil aerogels (BCCA). The BCCA, featuring high porosity and a hierarchical porous structure, demonstrated exceptional performance in oil–water separation applications. Specifically, it exhibited a high adsorption capacity for organic solutions (39 ∼ 117 g/g) and oils (32 ∼ 41 g/g), respectively, along with excellent selectivity, rapid adsorption time of approximately 30s, and good reuse capability, maintaining an adsorption efficiency of 85 %. These remarkable properties can be attributed to the exceptional hydrophobicity of the BCCA, with a contact angle of 134°, and the rapid capillary action facilitated by the helical network structure. The use of tea waste-derived carbon coils as a precursor for producing efficient and sustainable carbon coil aerogels presents a promising solution for environmental remediation, particularly in oil–water separation applications. This research addresses the issue of wastewater contamination and contributes to the utilization of tea waste, a readily available and abundant biomass resource, in the development of value-added materials for environmental sustainability.

Binary transition metal sulfides MoS2–NiS2 anchored on biomass-derived carbon for improved performance of lithium–sulfur batteries

The poor electrical conductivity of sulfur and electrochemically active solid-state products (Li2Sn, n = 1–3), and the shuttle effect have led to the low cycling stability of lithium-sulfur batteries and the low utilization of the sulfur cathode. In this work, 3D porous biomass-derived carbon material (KMC) was prepared from Miscanthus sinensis by KOH activation. The transition metal sulfide with excellent adsorption and catalytic characteristics was effectively combined with the conductive porous biomass-derived carbon material, and a KMC/MoS2−NiS2 composite material was obtained. The product was characterized by field emission scanning electron microscopy, X-ray diffraction, X-ray photoelectron spectroscopy, and Raman spectroscopy. Results show that MoS2−NiS2 nanoparticles can be uniformly distributed on the porous carbon material. Electrochemical measurements reveal that with an initial specific capacity of 1292 mA h g–1 at a current density of 0.1 C. After 400 cycles at 0.5 C, the specific capacity of KMC/MoS2−NiS2/S decays from 1007 to 814 mA h g–1. Thus, the capacity decay rate per cycle is about 0.054 %. This strategy provides a new idea for developing lithium−sulfur batteries with attractive performance.

A 3D porous carbon derived from waste jujube by one-step carbonization and activation for high-performance supercapacitors

Three-dimensional (3D) porous carbon doped with heterogeneous elements serves as electrode material displaying significant advantages in the improvement of the electrochemical performance of supercapacitors (SCs). Herein, one-step carbonization and activation produced a 3D porous carbon material derived from waste jujubes. The introduction of nitrogen doping enhances the wettability of the obtained carbon while contributing to pseudocapacitance. The 3D structure offers more ion-accessible surfaces and an increased surface area (943.3 m2 g−1), thereby facilitating ion migration and the establishment of an ion adsorption layer. Consequently, the specific capacitance of prepared porous carbon is 194.2 F g−1 (at 0.2 A g−1). Furthermore, prepared carbon delivered 92.7% retention after 10,000 cycles, indicating high stability. The obtained carbon shows outstanding electrochemical performance and potential as an electrode for supercapacitors.

Silk Fibroin Materials: Biomedical Applications and Perspectives.

The golden rule in tissue engineering is the creation of a synthetic device that simulates the native tissue, thus leading to the proper restoration of its anatomical and functional integrity, avoiding the limitations related to approaches based on autografts and allografts. The emergence of synthetic biocompatible materials has led to the production of innovative scaffolds that, if combined with cells and/or bioactive molecules, can improve tissue regeneration. In the last decade, silk fibroin (SF) has gained attention as a promising biomaterial in regenerative medicine due to its enhanced bio/cytocompatibility, chemical stability, and mechanical properties. Moreover, the possibility to produce advanced medical tools such as films, fibers, hydrogels, 3D porous scaffolds, non-woven scaffolds, particles or composite materials from a raw aqueous solution emphasizes the versatility of SF. Such devices are capable of meeting the most diverse tissue needs; hence, they represent an innovative clinical solution for the treatment of bone/cartilage, the cardiovascular system, neural, skin, and pancreatic tissue regeneration, as well as for many other biomedical applications. The present narrative review encompasses topics such as (i) the most interesting features of SF-based biomaterials, bare SF's biological nature and structural features, and comprehending the related chemo-physical properties and techniques used to produce the desired formulations of SF; (ii) the different applications of SF-based biomaterials and their related composite structures, discussing their biocompatibility and effectiveness in the medical field. Particularly, applications in regenerative medicine are also analyzed herein to highlight the different therapeutic strategies applied to various body sectors.