Formation Of Metal Nanoparticles Research Articles

Electrochemical Top-Down Synthesis of Nanostructured Electrocatalysts for Polymer Electrolyte Membrane Fuel Cells

Nanostructured catalysts are a promising class of materials to meet the requirements for the energy transition away from fossil fuels towards alternative, carbon-free, energy carriers, such as hydrogen. These catalyst materials boost the efficiency of energy conversion devices, such as fuel cells or electrolyzers, by accelerating their fundamental electrochemical reactions. Bottom-up synthetic routes for nanostructured materials often involve multiple synthesis steps and the use of surfactants, reducing agents or stabilizers. This results in complex and extensive synthesis protocols.[1] In recent years, a novel top-down synthesis approach to form metal nanoparticles has been established, in which bulk metal wires are immersed in an electrolyte and subsequently subjected to a high alternating potential. This leads to the generation of nanoparticles dispersed in the electrolyte.[2] There is no need for reducing agents, surfactants, or precursor solutions. The complete synthesis can be performed in one pot involving one main step with consequent washing and drying of the nanoparticles.In this study, we synthesized Pt-based nanoparticles supported on Vulcan® carbon support (Pt/C) and tested their electrochemical activity towards the oxygen reduction reaction (ORR) for polymer electrolyte membrane fuel cells (PEMFCs). Firstly, we elucidated the influence of synthesis parameters such as potential amplitude, frequency, electrolyte composition, and concentration on the size and shape of Pt nanoparticles.[3] We continued with the synthesis of more complex nanostructures, such as Pt alloy nanoparticles. This introduces strain and ligand effects at the surface of the nanoparticles, which increases the electrocatalytic activity for the ORR. We demonstrated the facile, simple, and surfactant-free synthesis of highly active PtxPr/C[4] and PtxCu/C, as two examples for Pt alloy catalysts for the ORR, and give an outlook on other systems, such as PtxGd/C.

An Overview of Heterogeneous Catalysts Based on Hypercrosslinked Polystyrene for the Synthesis and Transformation of Platform Chemicals Derived from Biomass.

Platform chemicals, also known as chemical building blocks, are substances that serve as starting materials for the synthesis of various value-added products, which find a wide range of applications. These chemicals are the key ingredients for many fine and specialty chemicals. Most of the transformations of platform chemicals are catalytic processes, which should meet the requirements of sustainable chemistry: to be not toxic for humans, to be safe for the environment, and to allow multiple reuses of catalytic materials. This paper presents an overview of a new class of heterogeneous catalysts based on nanoparticles of catalytically active metals stabilized by a polymer matrix of hypercrosslinked polystyrene (HPS). This polymeric support is characterized by hierarchical porosity (including meso- and macropores along with micropores), which is important both for the formation of metal nanoparticles and for efficient mass transfer of reactants. The influence of key parameters such as the morphology of nanoparticles (bimetallic versus monometallic) and the presence of functional groups in the polymer matrix on the catalytic properties is considered. Emphasis is placed on the use of this class of heterogeneous catalysts for the conversion of plant polysaccharides into polyols (sorbitol, mannitol, and glycols), hydrogenation of levulinic acid, furfural, oxidation of disaccharides, and some other reactions that might be useful for large-scale industrial processes that aim to be sustainable. Some challenges related to the use of HPS-based catalysts are addressed and multiple perspectives are discussed.

Effect Of Microwave In The Green Synthesis Of Colloidal Bismuth Nanoparticles

In this study, bismuth nanoparticles were synthesized and prepared using citrus aurantifolia green synthesis method. The effect of microwave heating was examined. Citrus aurantifolia was used to reduce metal ions and nanoparticle formation due to the presence of various biomolecules needed. microwave was chosen because it can accelerate and form more stable nanoparticles. Bismuth nanoparticles were successfully synthesized with UV-Vis wavelength at 276 nm and nanoparticle average size is 4.66 nm. This result also shows a better TEM result image when with microwave because there is no impurity from bioreductor.

Single-Atom Catalysts for Selective Oxygen Reduction: Transition Metals in Uniform Carbon Nanospheres with High Loadings.

Transition metal single-atom catalysts (SACs) in uniform carbon nanospheres have gained tremendous interest as electrocatalysts owing to their low cost, high activity, and excellent selectivity. However, their preparation typically involves complicated multistep processes that are not practical for industrial use. Herein, we report a facile one-pot method to produce atomically isolated metal atoms with high loadings in uniform carbon nanospheres without any templates or postsynthesis modifications. Specifically, we use a chemical confinement strategy to suppress the formation of metal nanoparticles by introducing ethylenediaminetetraacetic acid (EDTA) as a molecular barrier to spatially isolate the metal atoms and thus generate SACs. To demonstrate the versatility of this synthetic method, we produced SACs from multiple transition metals, including Fe, Co, Cu, and Ni, with loadings as high as 3.87 wt %. Among these catalytic materials, the Fe-based SACs showed remarkable catalytic activity toward the oxygen reduction reaction (ORR), achieving an onset and half-wave potential of 1.00 and 0.831 VRHE, respectively, comparable to that of commercial 20 wt % Pt/C. Significantly, we were able to steer the ORR selectivity toward either energy generation or hydrogen peroxide production by simply changing the transition metal in the EDTA-based precursor.

Fe-Co Alloy Nanoparticles Dispersed in Polymer-Derived Carbon Support: Effect of Initial Polymer Nature on the Size, Structure and Magnetic Properties.

Fe-Co alloy nanoparticles with different sizes, supported by carbon derived from several polymers, namely polyacrylonitrile, polyvinyl alcohol and chitosan, have been synthesized by a one-pot method involving simultaneous metal nanoparticle formation and polymer carbonization. The method involves the joint dissolution of metal salts and a polymer, followed by annealing of the resulting dried film. Detailed XRD analysis confirmed the formation of Fe-Co alloy nanoparticles in each sample, regardless of the initial polymer used. Transmission electron microscopy images showed that the Fe-Co nanoparticles were all spherical, were homogeneously distributed within the carbon support and varied by size depending on the initial polymer nature and synthesis temperature. Fe-Co nanoparticles supported by polyacrylonitrile-derived carbon exhibited the smallest size (6-12 nm), whereas nanoparticles on chitosan-derived carbon support were characterized by the largest particle size (13-38 nm). The size dependence of magnetic properties were studied by a vibrating sample magnetometer at room temperature. For the first time, the critical particle size of Fe-Co alloy nanoparticles with equiatomic composition has been experimentally determined as 13 nm, indicating the transition of magnetic properties from ferromagnetic to superparamagnetic.

Revitalizing platinum: Alkali-promoted formation of active metallic nanoparticles from inert Pt entities for enhanced benzene combustion

Pt-based catalysts play a crucial role in the catalytic combustion of benzene. Previous studies have highlighted the significance of metal Pt atoms as the active phase in benzene combustion, while oxidized Pt sites exhibit lower activity. In practical catalysts synthesized through wet chemical methods, a range of metal species is present, including highly dispersed oxidized metal atoms, small oxidized metal clusters, and metal nanoparticles. This paper explores an effective strategy to enhance metal utilization and develop high-performance platinum-based catalysts for benzene catalytic combustion by introducing alkali metals. This approach transforms low-activity oxidized metal atoms and small oxidized metal clusters into active small metal nanoparticles. The introduction of K-O groups displaces Pt from oxygen vacancy trapping sites on antimony-doped tin oxide (ATO) support, enhancing Pt mobility and converting them into active metallic Pt nanoparticles, ultimately improving benzene combustion. These findings highlight the role of alkali metals in promoting catalytic activity and provide insights for designing high-performance noble-metal-based catalysts.

Preparation of Dual‐activity Enzyme‐metal‐nanoparticles Conjugate Catalysts for Cascade Processes

AbstractThe fabrication of novel systems where enzymatic and metallic actives sites directly interact represents an elegant strategy for sustainable processes. One of the new strategies involves the in situ formation of metal nanoparticles on a protein network as scaffold. This biological entity is the key element because it conserves the biological catalytic efficiency and induces the final metallic nanoparticles generation on the structure. This method allows to obtain bifunctional enzyme‐metallic catalysts with excellent versatility and efficiency in a different reaction and experimental conditions. In this concept article, the relevant aspects in terms of fabrication of enzyme‐metal nanoparticles hybrids and recently reported examples of successful application in cascade processes will be described.

From biomolecules to biogeochemistry: Exploring the interaction of an indigenous bacterium with gold

Specialised microbial communities colonise the surface of gold particles in soils/sediments, and catalyse gold dissolution and re-precipitation, thereby contributing to the environmental mobility and toxicity of this ‘inert’ precious metal. We assessed the proteomic and physiological response of Serratia proteamaculans, the first metabolically active bacterium enriched and isolated directly from natural gold particles, when exposed to toxic levels of soluble Au3+ (10 μM). The results were compared to a metal-free blank, and to cultures exposed to similarly toxic levels of soluble Cu2+ (0.1 mM); Cu was chosen for comparison because it is closely associated with Au in nature due to similar geochemical properties. A total of 273 proteins were detected from the cells that experienced the oxidative effects of soluble Au, of which 139 (51%) were upregulated with either sole expression (31%) or had synthesis levels greater than the Au-free control (20%). The majority (54%) of upregulated proteins were functionally different from up-regulated proteins in the bacteria-copper treatment. These proteins were related to broad functions involving metabolism and biogenesis, followed by cellular process and signalling, indicating significant specificity for Au. This proteomic study revealed that the bacterium upregulates the synthesis of various proteins related to oxidative stress response (e.g., Monothiol-Glutaredoxin, Thiol Peroxidase, etc.) and cellular damage repair, which leads to the formation of metallic gold nanoparticles less toxic than ionic gold. Therefore, indigenous bacteria may mediate the toxicity of Au through two different yet simultaneous processes: i) repairing cellular components by replenishing damaged proteins and ii) neutralising reactive oxygen species (ROS) by up-regulating the synthesis of antioxidants. By connecting the fields of molecular bacteriology and environmental biogeochemistry, this study is the first step towards the development of biotechnologies based on indigenous bacteria applied to gold bio-recovery and bioremediation of contaminated environments.

Role of Kinetics and Thermodynamics in Controlling the Crystal Structure of Nickel Nanoparticles Formed on Reduced Graphene Oxide: Implications for Energy Storage and Conversion Applications

Ultrafast heating has emerged recently to speed up the synthesis processes of nanoparticles and control their morphology. However, it is not clear how the heating rate affects the formation of metal nanoparticles, particularly those formed on substrates. Here, we explored the formation of nickel (Ni) nanoparticles on graphene oxide (GO) substrates under slow (20 °C/min) and ultrafast (103 °C/s) heating rates. The experiments were performed in situ on heating microchip devices using an aberration-corrected transmission electron microscope. Interestingly, the GO structure was the most effective in controlling the stability of nanoparticles when ultrafast heating was employed, leading to a hexagonally close-packed Ni phase (hcp-Ni) because of less lattice mismatch with the graphitic substrate. On the contrary, fcc-Ni nanoparticles formed under a slow heating process where no strong correlation with the GO crystal structure was observed. Additionally, ultrafast heating resulted in smaller-size nanoparticles which could be ascribed to rapid reduction, nucleation rate, and higher diffusion barrier of hcp-Ni crystals on rGO. Nevertheless, the stability of the crystal structure of the nickel nanoparticles remains unaffected by their size. These results indicate the crucial role of the substrate on crystal structure during the nonequilibrium processing of materials and the competing effects of thermodynamics versus kinetics in creating novel phases of materials for energy storage and conversion applications.

PENENTUAN KANDUNGAN ANTIOKSIDAN DAN FENOLIK TOTAL DARI EKSTRAK TUMBUHAN SEBAGAI BIOREDUKTOR DALAM PEMBENTUKAN NANOPARTIKEL PERAK

The formation of metal nanoparticles (silver, gold, platinum) by biological methods (green synthesis) has advantages over chemical and physical methods because it is easier, faster, simpler, and environmentally friendly. One of the substances used in this method is plant extracts. The presence of secondary metabolites that act as antioxidants such as phenolics and flavonoids play roles in the formation of silver nanoparticles. In this study, phytochemical screening was carried out from several herbal plants as bioreductors in the formation of silver nanoparticles, such as Phyllanthus buxifolius, Pachira aquatica, Peperomia pellucida, Ageratum conyzoides, and Piper crocatum leaf extracts. The total antioxidant content was determined using the modified phenanthroline method, and the total phenolic content determined using the Folin-Ciocalteu method. The formation of silver nanoparticles was carried out by mixing silver nitrate solution with each plant extract. Colloidal silver nanoparticles formed were then measured for their absorption spectra. The results of the antioxidant content of the five consecutive samples were 26,90 ± 0,19; 26,09 ± 0,14; 18,25 ± 0,02; 42,76 ± 0,14; dan 30,94 ± 0,14 mg AA/g, while the total phenolic contents were 48,44 ± 0,45; 21,08 ± 0,92; 17,42 ± 0,27; 57,71 ± 0,47; dan 49,83 ± 0,60 mg GA/g. Silver nanoparticles mediated by Ageratum conyzoides leaf extracts provided the highest absorbance value compared to other plants. The antioxidants and phenolic contained in the extract acts as reducing agent from silver ions into silver nanoparticles.

Green synthesis, characterization and antibacterial activity of Tin (IV) oxide nanoparticles using root extract of Cassia tora

Synthesis of nanoparticles via green resources is a pollutant free, easy, ecofriendly, and low cost method. Nanoparticles synthesized by using plant materials are generally non-toxic. Aqueous root extract of plant, Cassia tora showed the presence of phytochemical constituents like alkaloids, flavonoids, phenols, tannins, saponins etc. which are directly involved in the reduction of metal salts hence forming metal nanoparticles. Thermal treatment of these metal nanoparticles changes them to their oxides. Tin (IV) oxide nanoparticles prepared via this route were first characterized and then evaluated for their antibacterial potential against three species of Gram negative bacteria viz., Salmonella typhi, Escherichia coli &Shigella flexineri and two speices of Gram positive bacteria viz. Bacillus cereus & Staphylococcus aureus. The current study reports the synthesis and characterization of Tin (IV) oxide nanoparticles using Cassia tora root extract.Synthesized nanoparticles were evaluated for their antibacterial activity. Results of antimicrobial activity showed excellent antibacterial property against Gram negative bacteria than Gram positive bacteria. Research has proved that green methods are more effective for generation of nanoparticles than the traditional methods, used in past as there are less chances of failure and shows enhanced biological activity.

Atomically Dispersed NiNx Site with High Oxygen Electrocatalysis Performance Facilely Produced via a Surface Immobilization Strategy

Nonprecious-metal heterogeneous catalysts with atomically dispersed active sites demonstrated high activity and selectivity in different reactions, and the rational design and large-scale preparation of such catalysts are of great interest but remain a huge challenge. Current approaches usually involve extremely high-temperature and tedious procedures. Here, we demonstrated a straightforward and scalable preparation strategy. In two simple steps, the atomically dispersed Ni electrocatalyst can be synthesized in a tens grams scale with quantitative yield under mild conditions, and the active Ni sites were produced by immobilizing preorganized NiNx complex on the substrate surface via organic thermal reactions. This catalyst exhibits excellent catalysis performances in both oxygen evolution and reduction reactions. It also exhibited tunable catalysis activity, high catalysis reproducibility, and high stability. The atomically dispersed NiNx sites are tolerant at high Ni concentration, as the random reactions and metal nanoparticle formation that generally occurred at high temperatures were avoided. This strategy illustrated a practical and green method for the industrial manufacture of nonprecious-metal single-site catalysts with a predictable structure.

Litchi‐derived platinum group metal‐free electrocatalysts for oxygen reduction reaction and hydrogen evolution reaction in alkaline media

AbstractWithin the framework of the circular economy, the waste litchi's skins were upgraded and transformed into electrocatalysts for oxygen reduction reaction (ORR) and hydrogen evolution reaction (HER). The waste litchi's skins were pyrolyzed, activated, and then used as carbon support for fabricating metal–nitrogen–carbons (M–N–Cs) which belong to a promising class of platinum group metal‐free electrocatalysts. The activated char was functionalized with transition metal (Fe, Ni, and Co)‐ phthalocyanine (Pc) in monometallic and bimetallic fashion by subjecting it to a thermal treatment at 600 and 900°C. The samples functionalized at 900°C showed higher performance for HER due to the formation of metal nanoparticles, whereas the samples functionalized at 600°C showed higher performance for ORR. Particularly, sample Ni–Co 900 had an overpotential of −0.38 V for HER, while the sample Fe 600 was the most active electrocatalyst for ORR by demonstrating the onset potential of ∼0.9 V (a half‐wave potential of ∼0.81 V) with the least production of unwanted peroxide anion.

Ex-Solution Hybrids Functionalized on Oxide Nanofibers for Highly Active and Durable Catalytic Materials

Ex-solution catalysts containing spontaneously formed metal nanoparticles socketed on the surface of reservoir oxides have recently been employed in various research fields including catalysis and sensing, due to the process efficiency and outstanding chemical/thermal stability. However, since the ex-solution process accompanies harsh reduction heat treatment, during which many oxides undergo phase decomposition, it restricts material selection and further advancement. Herein, we propose an elaborate design principle to uniformly functionalize ex-solution catalysts at porous oxide frameworks via an electrospinning process. As a case study, we selected the ex-solved La0.6Ca0.4Fe0.95Co0.05-xNixO3-δ (x = 0, 0.025 and 0.05) and SnO2 nanofibers as ex-solution hybrids and main frameworks, respectively. We confirmed superior dimethyl sulfide (C2H6S) gas sensing characteristics with excellent long-cycling stability. In particular, the high catalytic activities of ex-solved CoNiFe ternary nanoparticles, strongly socketed on reservoir oxide, accelerate the spillover process of O2 to dramatically enhance the response toward sulfuric analytes with exceptional tolerance. Altogether, our contribution represents an important stepping-stone to a rational design of ex-solved particle-reservoir oxide hybrids functionalized on porous oxide scaffolds for a variety of applications.

AQUEOUS-PHASE HYDROGENATION OF FURFURAL IN THE PRESENCE OF SUPPORTED METALLIC CATALYSTS OF DIFFERENT TYPES. A REVIEW

Hydrogenation of furfural in the presence of heterogeneous catalysts has recently attracted increased interest as a method for the synthesis of oxygen-containing compounds of various classes based on renewable raw materials. The composition of the catalyst and the conditions of its preparation essentially determine which of the routes of reductive conversions during the hydrogenation of furfural will be predominant. The present review summarizes and analyzes methods for controlling the physicochemical and functional properties of various metal catalysts with an emphasis on Pd-, Ni-, Co, and Cu-containing catalytic compositions, as the most common and practically significant in the hydrogenation of furfural. Many examples show the influence of the nature of the support, the composition of the active metal precursor, and the conditions for the formation of metal nanoparticles on the activity and selectivity of supported catalysts in the reductive conversions of furfural under aqueous-phase hydrogenation conditions. Promising directions of research on the development of methods for the synthesis of efficient catalysts with controlled functional properties in the hydrogenation of furfural are considered. The bibliography includes 127 references.

Enhanced electrochromic properties of Ag-incorporated WO3 nanocomposite thin films

WO3 nanocomposite thin films, in which metal nanoparticles are incorporated into a WO3 matrix, offer an enhanced electrochromic response speed with color neutrality. This article reports the structural, optical, and electrochemical properties of Ag nanoparticle-incorporated electrochromic WO3 thin films with different concentrations. Room-temperature-sputtered thin films using composite targets with a low Ag concentration exhibited a random distribution of small nanoparticles. In contrast, in the film with a higher Ag concentration, the particles were merged, resulting in a single or polycrystalline phase. Surface plasmon resonance peaks were observed in the absorption spectra of the Ag–WO3 composite films, indicating the formation of metallic nanoparticles, which was also confirmed via high-resolution transmission electron microscopy. The optical bandgaps decreased gradually from 3.15 eV for WO3-δ to 3.02 and 2.99 eV for W0.97Ag0.03O3-δ and W0.91Ag0.09O3-δ thin films, respectively. The W0.91Ag0.09O3-δ thin film showed a faster switching time of 2.6 s for coloring and 4.8 s for bleaching with a higher coloration efficiency of 66.52 cm2/C than those of the WO3-δ thin film, which were 3.8 s, 6.8 s, and 58.68 cm2/C, respectively. However, transmittance modulation in the W0.91Ag0.09O3-δ thin film was inferior to that in the other films. Furthermore, the W0.91Ag0.09O3-δ thin films were black in the colored state, whereas the bare WO3-δ and W0.97Ag0.03O3-δ thin films were Prussian blue, suggesting the realization of color neutrality through the incorporation of Ag nanoparticles.

Optical Super‐Localisation of Single Nanoparticle Nucleation and Growth in Nanodroplets

AbstractThe formation of metal nanoparticles (NPs) on surfaces by electrodeposition is of significant interest, particularly with a view to understand the early stages of nucleation and growth. Here, the combination of scanning electrochemical cell microscopy (SECCM) and interference reflection microscopy (IRM) is demonstrated to be a compelling approach for real‐time monitoring of NP dynamics within the SECCM meniscus‐electrode wetted area, through synchronous monitoring in the millisecond range of the electrochemical and optical signatures. Diffraction‐limited entities, undergoing phase changes at the electrode substrate, are readily highlighted and tracked in time, including the onset time for the appearance of NPs and their movement over time. The results strongly implicate the rapid formation, surface diffusion and aggregation of smaller entities (not detectable optically) to produce the larger electrodeposited NPs. By applying SECCM tips of different size, it is also possible to understand how the wetted area (meniscus size) plays a key role in the number of NPs formed, with small tip sizes allowing the formation of single NPs. The SECCM‐IRM approach is expected to be a powerful platform for the study of myriad phase‐formation processes at the nanoscale, particularly by drawing on the possibility of making hundreds or thousands of measurements in fresh surface locations through SECCM technology.

Light-Assisted Synthesis of Silver and Gold Nanoparticles by New Benzophenone Derivatives.

Benzophenone derivatives were evaluated as new photoinitiators in combination with triethylamine (TEA) and iodonium salt (Iod) for very rapid and efficient formation of metal nanoparticles in an organic solvent, by which silver and gold ions were reduced under light at 419 nm (photoreactor) with an irradiation intensity of 250 microwatts/cm2. The new benzophenone derivatives combined with TEA/Iod salt showed good production of metal nanoparticles (Au0 and Ag0) and a small size of nanoparticles of around 4-13 nm. The photochemical mechanisms for the production of initiating radicals were studied using cyclic voltammetry, where a negative ΔG of around -1.96 eV was obtained, which made the process favorable. The obtained results proved the formation of amine and phenyl radicals, which led to the reduction of gold III chloride or silver ions to the gold and silver NPs. The UV-vis spectroscopy technique was used as a very beneficial tool for the surface plasmon resonance band detection of metal nanoparticles. To sum up the results, we have observed that nanoparticles (NPs) were distributed differently in different photoinitiator systems and the particle size also changed by changing the system of initiation. In comparison to the system alone, not only were the nanoparticles smaller but they were also generated within a shorter period of irradiation time for the system BP\Iod\TEA. Finally, the quenching process of benzophenone fluorescence by the gold and silver nanoparticles was investigated.

Oriented attachment of carbon/cobalt-cobalt oxide nanotubes on manganese-doped carbon nanofibers for flexible symmetric supercapacitors

Electrodes for flexible supercapacitors were fabricated from manganese-doped carbon nanofibers (Mn-CNF) decorated with carbon-coated Co-CoOx (C/Co-CoOx) nanotubes. The Mn-doped polyacrylonitrile (PAN)–2-methylimidazole (2MI) solution was electrospun using optimized Mn concentrations and ZIF-67 was then surface loaded by wet impregnation with added polyvinylpyrrolidone (PVP). These ZIF-67 loaded Mn-fibers, when annealed, resulted in carbon-coated C/Co-CoOx nanotubes on the Mn-CNF surface. In the presence of PVP, ZIF-67 oriented attachment occurs, forming evenly dispersed CoOx particles even after high temperature annealing. XRD spectra exhibit the formation of metallic Co nanoparticles (NPs), whereas Raman spectra and XPS indicate Co particle oxidation. A carbon coating limits the oxidation of Co; thus, the particles are called C/Co-CoOx. A symmetric supercapacitor cell prepared using the CNFs decorated with C/Co-CoOx using an aqueous electrolyte has a capacitance of 1263 mF⋅cm−2 at a current density of 0.25 mA⋅cm−2 and a wide potential window of 1.4 V for the optimal case. Long-term cycling showed 110 % capacitance retention after 10,000 cycles. Moreover, bending tests and powering LEDs demonstrated the flexibility and improved charge storage of the prepared nanofiber electrodes.

Strategies for Integrating Metal Nanoparticles with Two‐Photon Polymerization Process: Toward High Resolution Functional Additive Manufacturing

AbstractThis study reports the successful fabrication of complex 3D metal nanoparticle–polymer nanocomposites using two‐photon polymerization (2PP). Three complementary strategies are detailed: in situ formation of metal nanoparticles (MeNPs) through a single‐step photoreduction process, integration of pre‐formed MeNPs into 2PP resin, and site‐selective MeNPs decoration of 3D 2PP structures. In the in situ formation strategy, a phase‐transfer method is applied to transfer silver and copper ions from an aqueous phase into a toluene solvent to disperse them in photoreactive monomers.The addition of a photosensitive dye, coumarin 30, facilitated the reduction of silver ions and improved the distribution of silver nanoparticles (AgNPs). This strategy is successfully used to produce other MeNPs, such as Cu and Au. The integration of pre‐formed MeNPs enabled highly controlled NP size distribution within the 2PP 3D structures with high‐fidelity To enable selective decoration of 2PP 3D surfaces with MeNPs, a multimaterial strategy is developed, with one of the resins designed for thiol‐ene reaction, which demonstrated selective binding to AuNPs. The successful development of complementary strategies for integration of MeNPs into 2PP resins offers exciting opportunities for fabrication of MeNP composites with sub‐micron resolution for applications from photonics to metamaterials and drug delivery.