Abiotic and biotic-controlled nanomaterial formation pathways within the Earth’s nanomaterial cycle
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Environmental Sciences & Ecology↗
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Electrified vapour deposition at ultrahigh temperature and atmospheric pressure for nanomaterials synthesis
Vapour-phase synthesis methods have shown promise for the scalable synthesis of nanomaterials and coatings. However, the vaporization of different precursors for the synthesis of a broad nanomaterial space, particularly at atmospheric pressure, while maintaining compositional and structural control of the final product is challenging. Here we report the generation of an ultrahigh-temperature atomic vapour at atmospheric pressure based on electrified heating, for the growth of multi-elemental nanomaterials and thin films. This process relies on a reactor design whereby solid-state precursors are vaporized within a semi-confined space beneath an electrified heater that can reach ~3,000 K. The proximity of the heater rapidly breaks down the bonds of metal salt precursors and decomposes them into an atomic vapour that expands into a high-temperature (>2,000 K), highly reactive and high-flux vapour (10 21 –10 22 atoms per cm 2 per second) that travels upwards in a directional flow. When mixed with entrained ambient gases, the highly reactive atomic species rapidly nucleate and grow into the desired final products, including alloys, oxides, sulfides and thin films, which can be deposited on a low-temperature substrate. This EVD approach can synthesize a broad range of functional nanomaterials at atmospheric pressure, including single-phase multi-elemental nanomaterials formed under thermodynamically non-equilibrium conditions.
36 MATERIALS SCIENCE↗
Engineering Escherichia coli for Urease-Driven Synthesis of Metal Oxide Nanomaterials
The development of functional nanomaterials with controlled morphologies is essential for advancements in medicine, electronics and computing, energy, catalysis, and environmental applications. However, conventional synthesis methods often demand high energy input and pose significant environmental challenges. Urease-based biomineralization presents an efficient, eco-friendly alternative for nanomaterial production under mild conditions. In this study, we engineered Escherichia coli ( E. coli ) to express a urease gene cluster from Sporosarcina pasteurii using CRAGE-Duet technology. The engineered strain successfully synthesized calcium carbonate and calcium phosphate crystals. Expanding the approach, we synthesized metal oxide nanoparticles, including hematite (Fe 2 O 3 ), and nanocrystalline anatase titanium dioxide (TiO 2 ). These nanomaterials were characterized by electron microscopy, demonstrating the potential of E. coli as a sustainable and versatile platform for green nanomaterial synthesis.
bacteria↗
Assembly of Metalloporphyrin Peptoids into Crystalline Nanomaterials as a Multifunctional System for Biomimetic Catalysis and Sensing
While natural enzymes excel at catalysis and sensing, they often suffer from high cost and low stability in applications outside living systems. Among tremendous efforts made toward the design and synthesis of catalytic biomimetic materials, the approach of using crystalline nanomaterials assembled from sequence-defined polymers has emerged as a promising strategy. Herein, we report the assembly of metalloporphyrin peptoids into crystalline nanomaterials as a multifunctional system for biomimetic catalysis and sensing. The precise spatial positioning of covalently attached porphyrins within crystalline peptoid nanomaterials enables the mimicry of several enzyme active sites, including phosphotriesterase and horseradish peroxidase, for efficient catalytic hydrolysis and oxidation reactions. Additionally, the high programmability of these peptoid crystalline materials enables the creation and tuning of the active site microenvironment for enhanced catalytic activity. We further demonstrate the integration of responsive organic dyes into catalytic peptoid assemblies to achieve both detection and degradation of chemical warfare agent (CWA) mimics, even in the vapor phase. In conclusion, we expect this multifunctional system to provide tremendous opportunities in biomimetic catalysis and sensing, including the detoxification and detection of CWAs.
Catalysts↗
Electron Microscopy Studies of Soft Nanomaterials
This review highlights recent efforts on applying electron microscopy (EM) to soft (including biological) nanomaterials. We will show how developments of both the hardware and software of EM have enabled new insights into the formation, assembly, and functioning (e.g., energy conversion and storage, phonon/photon modulation) of these materials by providing shape, size, phase, structural, and chemical information at the nanometer or higher spatial resolution. Specifically, we first discuss standard real-space two-dimensional imaging and analytical techniques which are offered conveniently by microscopes without special holders or advanced beam technology. The discussion is then extended to recent advancements, including visualizing three-dimensional morphology of soft nanomaterials using electron tomography and its variations, identifying local structure and strain by electron diffraction, and recording motions and transformation by in situ EM. On these advancements, we cover state-of-the-art technologies designed for overcoming the technical barriers for EM to characterize soft materials as well as representative application examples. Here, the even more recent integration of machine learning and its impacts on EM are also discussed in detail. With our perspectives of future opportunities offered at the end, we expect this review to inspire and stimulate more efforts in developing and utilizing EM-based characterization methods for soft nanomaterials at the atomic to nanometer length scales in academic research and industrial applications.
Imaging↗
Tuning 3-D Nanomaterial Architectures Using Atomic Layer Deposition to Direct Solution Synthesis
The ability to synthesize nanoarchitected materials with tunable geometries provides a means to control their functional properties, with applications in biological, environmental, and energy fields. To this end, various bottom-up and top-down synthesis processes have been developed. However, many of these processes require prepatterning or etching steps, making them challenging to scale-up to complex, nonplanar substrates. Furthermore, the ability to integrate nanomaterials into hierarchical arrays with precise control of feature spacing and orientation remains a challenge. One approach to overcome these patterning challenges is the use of surface modification layers to guide the resulting geometry of nanomaterial architectures grown from the substrate. A powerful strategy to accomplish this is what we will refer to as “surface-directed assembly,” where the resulting geometric parameters (feature size, shape, orientation) are predetermined by the initial surface layer. In particular, the use of Atomic Layer Deposition (ALD) to form a surface layer, followed by solution-based growth processes, has the ability to synthesize architected structures with tunable geometries on complex, nonplanar surfaces. Over the past decade, we have reported a series of studies where surface-directed assembly is used to synthesize ZnO nanowires (NWs) on top of a variety of substrates. In this case, a thin film of ZnO is deposited onto the substrate using ALD, which can guide the NW diameter, spacing, and angular orientation with respect to the substrate by controlling epitaxial relationships. Furthermore, we have shown that by depositing a submonolayer overcoat of a secondary material (e.g., amorphous TiO 2 ), nucleation sites are partially blocked, which can further tune the spacing between nanowires while minimizing changes to their other geometric properties. This approach can be used to generate multilevel hierarchical structures, such as hyperbranched NW arrays with tunable control of each level of hierarchy using ALD. Finally, we have demonstrated that the tunable control of geometric parameters can be scaled-up to curved, nonplanar substrates. This highlights the power of ALD to conformally and uniformly deposit the seed layers on complex substrates with subnanometer precision. To complement these seeded hydrothermal approaches, we expanded this strategy to include conversion chemistry of the initial ALD seed layers. For example, by replacing ZnO with Al 2 O 3 as the seed layer without changing the hydrothermal growth conditions, Al–Zn layered-double hydroxide nanosheets can be formed instead of nanowires. In another example of conversion chemistry, a solution anion-exchange process was used to incorporate sulfur into ALD metal oxide films. In both of these conversion processes, the properties of the initial ALD film enabled tuning of the resulting nanostructure geometry. In this Account, we describe the use of ALD to guide the growth of diverse nanomaterial systems, with tunable control over their geometry and composition. We further show how these approaches can be used to tune functional properties for a range of applications, including superomniphobic surfaces, antibiofouling coatings, and photocatalysis. In conclusion, we conclude with an outlook on how the combination of ALD and solution synthesis can enable future directions in scalable nanomanufacturing to overcome the limitations of traditional top-down and bottom-up approaches.
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
Nanomaterial-Engineered Surfaces for Decontamination of Water Resources
Aggregation-dependent shifts in plasmon frequency (colorimetric sensor); • Local refractive index-dependent shifts in plasmon frequency; • Inelastic (surface-enhanced Raman) light scattering; • Elastic (Rayleigh) light scattering CONCLUSIONS Generate unique classes of nanoscale materials for environmental stewardship applications o Characterization of nanomaterials provides understanding of structural properties for sorption of contaminants o Surface charge influences interaction between nanomaterial and contaminant o Surface charge can be modified to allow for more contaminant sorption • Demonstrate innovative nanomaterial science and technology solutions that meet our environmental stewardship needs: • Detect contaminants • Sequester contaminants
Murph, Simona E. [Savannah River National Laborato↗
Theoretical Calculation Study of Nanomaterials
In recent years, theoretical simulations using computational physics and chemistry models have been used widely to predict the physical, chemical, and structural properties of nanomaterials. To reflect such rapid progress, two Special Issues on the theoretical study of nanomaterials were published. The 36 articles collected cover broad re-search fields and applications. In this Editorial, we provide an overview of these pub-lications and summarize the main findings. Based on these research outcomes, we lay out some future research directions.
First-principles calculations↗
Advances in the photon avalanche luminescence of inorganic lanthanide-doped nanomaterials
Photon avalanche (PA)—where the absorption of a single photon initiates a ‘chain reaction’ of additional absorption and energy transfer events within a material—is a highly nonlinear optical process that results in upconverted light emission with an exceptionally steep dependence on the illumination intensity. Over 40 years following the first demonstration of photon avalanche emission in lanthanide-doped bulk crystals, PA emission has been achieved in nanometer-scale colloidal particles. The scaling of PA to nanomaterials has resulted in significant and rapid advances, such as luminescence imaging beyond the diffraction limit of light, optical thermometry and force sensing with (sub)micron spatial resolution, and all-optical data storage and processing. In this review, we discuss the fundamental principles underpinning PA and survey the studies leading to the development of nanoscale PA. Finally, we offer a perspective on how this knowledge can be used for the development of next-generation PA nanomaterials optimized for a broad range of applications, including mid-IR imaging, luminescence thermometry, (bio)sensing, optical data processing and nanophotonics.
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
Microwave Catalysis for Process Intensified Modular Production of Carbon Nanomaterials from Natural Gas
The objective of this project was to develop a novel, low-cost process intensified modular process to directly convert flare gas or stranded gas to carbon nanomaterials and co-product hydrogen (H 2 ) with high conversion, selectivity, and stability. The proposed project was based on our exciting exploratory research on a patent pending technology for one-step conversion of natural gas to carbon nanotubes (CNTs) and carbon fibers (CNFs) without emitting CO 2 : CH 4 → H 2 + C (CNT, Carbon Fibers).
03 NATURAL GAS↗
Probing the high-pressure densification of amorphous silica nanomaterials using SBA-15: An investigation into the paradoxical nature of the first sharp diffraction peak
The densification and X-ray scattering of mesoporous silica (SBA-15) were measured simultaneously under gigapascal (GPa) pressures. The results are compared to previous work on amorphous silica (aSiO 2 ) and demonstrate the feasibility of measuring the densification of aSiO 2 nanomaterials with small angle X-ray scattering (SAXS) in-situ in a diamond anvil cell. Compared to fused silica, the position of the SBA-15 first sharp diffraction peak (FSDP) is 7 times more sensitive to pressure and has a transition in its pressure dependance at a lower pressure (~2 GPa vs.~13 GPa). SBA-15 has two densification regimes, low-density amorphous and highdensity amorphous, which have equations of state comparable to low-density amorphous and high-density amorphous fused silica. Further, the transition between these two regimes occurs at a lower pressure than for fused silica (~1.5 GPa vs.~13 GPa). The results suggest that there is no direct relationship between the FSDP position and the aSiO 2 density during compression.
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
Plasmon-Induced Resonance Energy Transfer in Hybrid Nanomaterials
Plasmon-induced resonance energy transfer (PIRET) has emerged as a powerful mechanism for harnessing and redirecting plasmon energy before it dissipates into hot carriers or heat. By matching plasmon resonance frequencies with acceptor absorption bands, PIRET extends plasmon-driven processes beyond the charge transfer pathway, enabling selective energy flow into excitonic transitions. Here, this review highlights important progress in elucidating the fundamental plasmon decay processes and transitioning them into hybrid nanomaterials under PIRET. Employing specialized single-particle spectroscopic techniques based on scattering, extinction, and emission enables demonstration of PIRET in the face of competing mechanisms, such as interfacial charge transfer and thermalization. Finally, we complete this review by addressing strategies for active modulation of PIRET and present applications, ranging from plasmon photocatalysis to intracellular biochemical sensing.
Energy transfer↗
Assembled peptoid crystalline nanomaterials as carbonic anhydrase mimics for promoted hydration and sequestration of CO 2
Carbonic anhydrase (CA) mimics have received significant attention due to their promising applications in the enhanced hydration and sequestration of CO 2 . Herein, we report the assembly of sequence-defined peptoids into crystalline nanomaterials with controlled microenvironment of active sites as CA mimics for promoted hydration and sequestration of CO 2 . By incorporating specific ligands into self-assembling peptoids and coordinating these ligands with metal cations, we synthesize a variety of crystalline nanosheets and nanotubes as efficient CA mimics comparable to natural bovine CA. Molecular dynamics simulations reveal the critical roles of peptoid-Zn 2+ binding energy and the active site local microenvironment on the catalytic performance of these CA mimics. CO 2 precipitation results show that these CA mimics promote the hydration and sequestration of CO 2 while retaining high thermal and chemical stabilities. This study offers essential guidance for the future design of high-performance CA-mimics suitable for applications in CO 2 capture and sequestration.
Chakma, Progyateg [Pacific Northwest National Labo↗
Deep-learning atomistic semi-empirical pseudopotential model for nanomaterials
The semi-empirical pseudopotential method (SEPM) has been widely applied to provide computational insights into the electronic structure, photophysics, and charge carrier dynamics of nanoscale materials. We present “DeepPseudopot”, a machine-learned atomistic pseudopotential model that extends the SEPM framework by combining a flexible neural network representation of the local pseudopotential with parameterized non-local and spin-orbit coupling terms. Trained on bulk quasiparticle band structures and deformation potentials from GW calculations, the model captures many-body and relativistic effects with very high accuracy across diverse semiconducting materials, as illustrated for silicon and group III-V semiconductors. DeepPseudopot’s accuracy, efficiency, and transferability make it well-suited for data-driven in silico design and discovery of novel optoelectronic nanomaterials.
Lin, Kailai [University of California, Berkeley, C↗
Plasmonic pathway to hybrid nanomaterials through energy transfer
Plasmon-induced resonance energy transfer (PIRET) is a promising approach for plasmonic photocatalysis and energy conversion, but challenges include elucidating the mechanism and maximizing its efficiency, both of which are hampered by competing processes. Another challenge is demonstrating that PIRET can photoinitiate reactions that follow efficient pathways compared to bulk processes. We report a plasmon-induced route to plasmonic-polymer hybrid nanomaterials using in operando single-particle spectroelectrochemistry. An energy transfer efficiency of 40% is achievable when the spectral overlap between gold nanorod scattering and polymer absorption is maximized. We also show that PIRET-initiated polymerization proceeds through a different mechanism than bulk polymerization, supported by spectroscopic evidence and density functional theory calculations, highlighting efficient energy cascading from photon to plasmon to exciton and, lastly, to unconventional light-initiated chemistry.
Oh, Hyuncheol [University of Illinois Urbana-Champ↗
Green Synthesis of Multifunctional Nanomaterials
CONCLUSIONS • We demonstrate eco-friendly and green synthesis approaches of isotropic and anisotropic nanomaterials that meet our environmental stewardship needs: • Atom Economy: Maximize the incorporation of all materials used in a reaction into the final product. • Prevention: Prevent waste generation in the first place. • Less Hazardous Chemical Synthesis: Use and generate substances with low toxicity to humans and the environment. • Safer Solvents and Auxiliaries: Avoid or minimize the use of hazardous solvents.
Murph, Simona E. [Savannah River National Laborato↗
Establishing defect-property relationships for 2D-nanomaterials (Final technical report)
Studies of new families of two-dimensional nanomaterials (2DNMs) have established that they possess unique properties that diverge from those of their bulk counterparts. This project aimed to determine how tolerant 2DNMs are to extreme photon and particle fluxes and to identify the mechanisms governing their radiation response. Early work indicated that graphene is not as representative of other 2DNMs as previously assumed; however, the origin of this difference remained unclear. To address these knowledge gaps, this project investigated the physical processes occurring at multiple length scales in transition metal dichalcogenides (TMDs) and quantified their structural stability and property evolution under far-from-equilibrium conditions. In-situ and ex-situ ion and electron irradiations were performed to directly control and monitor defect formation in TMDs. Complementary density functional theory (DFT) and molecular dynamics (MD) simulations were employed to elucidate the mechanisms of defect generation and evolution. The outcomes of this work established mechanistic understanding of irradiation-induced defect formation in 2DNMs, quantified the radiation tolerance of TMDs, and built a fundamental knowledge base for correlating defect structures with material properties. Collectively, these results provide new insights into the stability of low-dimensional materials in extreme environments and enable the predictive design of radiation-tolerant 2DNMs.
2D materials↗
Modeling Carbon-Based Nanomaterials (CNMs) and Derived Composites and Devices
A review of different modeling techniques, specifically in the framework of carbon-based nanomaterials (CNMs, including nanoparticles such as graphene and carbon nanotubes—CNTs) and the composites and devices that can be derived from them, is presented. The article emphasizes that the overall performance of these materials depends on mechanisms that operate across different time and spatial scales, requiring tailored approaches based on the material type, size, internal structure/configuration, and the specific properties of interest. Far from attempting to cover the entire spectrum of models, this review examines a wide range of analysis and simulation techniques, highlighting their potential use, some of their weaknesses and strengths, and presenting the latest developments and some application examples. In this way, it is shown how modeling can provide key information for tailoring or designing new materials for specific components or systems or to obtain certain functionalities. At the same time, it is revealed to be an area constantly undergoing development and improvement, as evidenced by the progress made by various of these techniques and the new modeling approaches that have emerged in recent years.
Chiminelli, Agustίn (ORCID:0000000230312107)↗