Synthesis Of Inorganic Materials Research Articles

Synthesis of gold nanoparticles using silk sericin as a green reducing and capping agent

Various natural materials were used recently for the synthesis of gold nanoparticles (AuNPs). These natural materials are attracting attention because they are more environmentally friendly than conventional chemicals used for AuNP synthesis. Silk sericin (SS) is a protein that is removed during the silk degumming process, and it has been studied for the synthesis of several inorganic materials, such as hydroxyapatite and silica. The present study synthesized AuNPs using SS. To optimize the conditions for the synthesis of AuNPs, the effects of reaction pH, SS concentration, reaction time and temperature during the formation of AuNPs were monitored using visual observation, a UV–Vis spectrophotometer, and energy-filtered transmission electron microscopy (EF-TEM) analysis. When the concentration of HAuCl4 was 1 mM, the optimal conditions for synthesizing AuNPs were an SS concentration of 1 mg/ml, a reaction pH of 7, a reaction temperature of 70 °C and a reaction time of 12 h. The AuNPs prepared under the optimal conditions had a size of approximately 17 nm, and the particles were well dispersed. When ethanol was added, the secondary structure of SS transitioned to β-sheets, the size of the gold nanoparticles increased to approximately 20 nm, and the amount of AuNPs increased. Amino acids bearing a hydroxyl group or negative charge were effective in the synthesis of AuNPs, and SS has a high content of these amino acids. Therefore, SS reduced gold ions and induced the synthesis of AuNPs. High-resolution TEM (HR-TEM), energy-dispersive X-ray spectroscopy (EDS), and thermogravimetric analysis (TGA) revealed that SS remained in a form that capped the synthesized AuNPs.

Towards Predictive Synthesis of Inorganic Materials Using Network Science

Accelerating materials discovery is the cornerstone of modern technological competitiveness. Yet, the inorganic synthesis of new compounds is often an important bottleneck in this quest. Well-established quantum chemistry and experimental synthesis methods combined with consolidated network science approaches might provide revolutionary knowledge to tackle this challenge. Recent pioneering studies in this direction have shown that the topological analysis of material networks hold great potential to effectively explore the synthesizability of inorganic compounds. In this Perspective we discuss the most exciting work in this area, in particular emerging new physicochemical insights and general concepts on how network science can significantly help reduce the timescales required to discover new materials and find synthetic routes for their fabrication. We also provide a perspective on outstanding problems, challenges and open questions.

Solubilization and aggregation control of silica-polymerizing enzyme fused with a removable soluble protein

Silicatein, a silica-polymerizing enzyme, is an attractive and promising biocatalyst in many applications such as the synthesis of bio-functionalized inorganic materials under mild conditions. However, its unfavorable aggregation in aqueous media due to its intermolecular hydrophobic interactions causes difficulties in handling and applications. This study aimed to enhance the solubility of silicatein via fusion with a small soluble protein, ProS2. ProS2-Sil showed high solubility and stability in aqueous media for more than 24h. The aggregation property of ProS2-silicatein fusion protein (ProS2-Sil) was investigated with and without cleavage of ProS2 tag by site-specific protease. When ProS2 tag was removed, silicatein became aggregated, which was analyzed by transmission electron microscope and fluorescence microscope. ProS2-Sil and mature silicatein showed similar activities in silica polymerization. The present approach allows the utilization of silicatein in the fabrication of novel and functional inorganic biohybrid materials.

A Theoretical Perspective on Strategies for Modeling High Performance Nonlinear Optical Materials

Nonlinear optical (NLO) materials have spanned a large area of science and technology owning to their potential applications in optoelectronics. The invention of the first Ruby laser has sparked a fresh interest in the area of nonlinear optics. The computational designing and experimental synthesis of organic and inorganic NLO materials with higher order nonlinearities come into vogue in the field of materials science. To date, several strategies including metal ligand framework, push pull mechanism, diradical character, and so on have been devised to enhance the NLO response of materials. In addition, introduction of diffuse excess electrons is an efficient approach to design noncentrosymmetric materials for nonlinear optics. The current review highlights a systematic array of different computational studies (covering the last decade of intensive research work) for the theoretical designing of NLO materials. In the present review, theoretical designing from the simplest NLO material to the complex alkali, alkaline earth, transition, and superalkali doped nanomaterials is summarized. The emergence of excess electrons strategy has played a pivotal role in enhancing the NLO properties especially hyperpolarizabilities. We expect that this review will provide a better understanding of the NLO responses of nanoclusters, paving the way for the advancement of hi-tech NLO materials to meet the real challenges in optoelectronics.

Hypergolic Synthesis of Inorganic Materials by the Reaction of Metallocene Dichlorides with Fuming Nitric Acid at Ambient Conditions: The Case of Photocatalytic Titania

Hypergolic materials synthesis is a new preparative technique in materials science that allows a wide range of carbon or inorganic solids with useful properties to be obtained. Previously we have demonstrated that metallocenes are versatile reagents in the hypergolic synthesis of inorganic materials, such as γ-Fe2O3, Cr2O3, Co, Ni and alloy CoNi. Here, we go one step further by using metallocene dichlorides as precursors for the hypergolic synthesis of additional inorganic phases, such as photocatalytic titania. Metallocene dichlorides are closely related to metallocenes, thus expanding the arsenal of organometallic compounds that can be used in hypergolic materials synthesis. In the present case, we show that hypergolic ignition of the titanocene dichloride–fuming nitric acid pair results in the fast and spontaneous formation of titania nanoparticles at ambient conditions in the form of anatase–rutile mixed phases. The obtained titania shows good photocatalytic activity towards Cr(VI) removal (100% within 9 h), with the latter being dramatically enhanced after calcination of the powder at 500 °C (100% within 3 h). Notably, this performance was found to be comparable to that of commercially available P25 TiO2 under identical conditions. The cases of zirconocene, hafnocene and molybdocene dichlorides are discussed in this work, which aims to show the wider applicability of metallocene dichlorides in the hypergolic synthesis of inorganic materials (ZrO2, HfO2, MoO2).

Addressing the critical need for open experimental databases in materials science

With the HTEM, an open online database containing experimental synthesis and characterization data of thin film inorganic materials, Talley et al. (2021) lay a foundation for a new era of high-throughput materials design.

Hyaluronic-Acid-Based Organic-Inorganic Composites for Biomedical Applications.

Applications of natural hyaluronic acid (HYH) for the fabrication of organic-inorganic composites for biomedical applications are described. Such composites combine unique functional properties of HYH with functional properties of hydroxyapatite, various bioceramics, bioglass, biocements, metal nanoparticles, and quantum dots. Functional properties of advanced composite gels, scaffold materials, cements, particles, films, and coatings are described. Benefiting from the synergy of properties of HYH and inorganic components, advanced composites provide a platform for the development of new drug delivery materials. Many advanced properties of composites are attributed to the ability of HYH to promote biomineralization. Properties of HYH are a key factor for the development of colloidal and electrochemical methods for the fabrication of films and protective coatings for surface modification of biomedical implants and the development of advanced biosensors. Overcoming limitations of traditional materials, HYH is used as a biocompatible capping, dispersing, and structure-directing agent for the synthesis of functional inorganic materials and composites. Gel-forming properties of HYH enable a facile and straightforward approach to the fabrication of antimicrobial materials in different forms. Of particular interest are applications of HYH for the fabrication of biosensors. This review summarizes manufacturing strategies and mechanisms and outlines future trends in the development of functional biocomposites.

Triblock polyadenine probe-based electrochemical DNA sensor by integrating 3D DNAzyme walker and strand displacement for ultrasensitive and rapid detection of Pb2+

Electrochemical DNA sensors have exhibited excellent advantage for the ultrasensitive detection of trace targets. However, the multi-step electrode modification process for sensitivity improvement and low controllability of electrode assembly limit their further application. In this work, a novel triblock polyadenine probe-based electrochemical DNA sensor was established for ultrasensitive and rapid determination of Pb2+. In the presence of the target, copious double strands (LD) were obtained through DNAzyme walker and strand displacement reaction. Triblock polyadenine probe (TPP) was then utilized to specifically capture LD on the electrode surface and construct duplex carriers for intercalating methylene blue. Consequently, on account of the introducing of non-electrode-modification signal-recognition-amplification strategies and TPP, the proposed DNA sensor dispensed with complex electrode modifications. Meanwhile, high sensitivity was guaranteed due to multiple amplification strategies without any natural enzymes, special devices or synthesis of inorganic materials. Under the optimized conditions, multiple modules with coordinated combination achieved the detection limits of 0.039 pM, superior to most published methods. Considering the flexible design of DNA sequences, the sensing platform developed in this work could be applied in the detection of various targets.

Inorganic Synthesis Based on Reactions of Ionic Liquids and Deep Eutectic Solvents.

Ionic liquids and deep eutectic solvents are of growing interest as solvents for the resource‐efficient synthesis of inorganic materials. This Review covers chemical reactions of various deep eutectic solvents and types of ionic liquids, including metal‐containing ionic liquids, [BF4]−‐ or [PF6]−‐based ionic liquids, basic ionic liquids, and chalcogen‐containing ionic liquids. Cases in which cations, anions, or both are incorporated into the final products are also included. The purpose of this Review is to raise caution about the chemical reactivity of ionic liquids and deep eutectic solvents and to establish a guide for their proper use.

Biomineralization: Biomimetic Synthesis of Materials and Biomimetic Regulation of Organisms

AbstractThe review summaries our achievements in biomineralization. A new understanding of non‐classical nucleation is introduced, which highlights the formation of ionic clusters during the early mineral formation. This discovery directs to a new chemical concept of inorganic ionic oligomers and their crosslinking. Different from the conventional syntheses of inorganic materials, the inorganic ionic oligomers can be used as the conformable precursors to achieve moldable constructions, which arises from a fusion of classic inorganic and polymer chemistry by sharing the same process for the manufacture of materials. By using the inorganic oligomers, the biomimetic regenerations/ repairs of hard tissues such as tooth enamel and bone can be realized. And the advanced artificial materials superior over biological ones can be developed by inorganic‐organic co‐polymerization. Moreover, biomineralization is a tool for the integration of materials and biological organism. Our attempts demonstrate that the rationally designed materials‐biologicals can contribute to vaccine improvement, universal blood transfusion, and cancer treatment, etc. They follow a transformation of biomineralization study from biomimetic synthesis of materials to biomimetic modification of organisms and furthermore, start an understanding of chemical biological regulation by materials. What is the most favorite and original chemistry developed in your research group?The discovery of ionic oligomers and their crosslinking following a new concept of inorganic ionic polymerization.How do you get into this specific field? Could you please share some experiences with our readers?I got into the field of biomineralization when I was a graduate student. A challenge in biomineralization community is how we can achieve a moldable construction of inorganic materials (biominerals). Fortunately, we observed the formation of ultrasmall ion aggregates at the early nucleation strategy. This finding subsequently directed to our exploration of ionic oligomers and the most important key was a new start of this inorganic study upon a view of polymer chemistry.How do you supervise your students?I keep on asking my students two questions: 1) What unsolvable problem can you solve for our society by your study? 2) What new understanding can you contribute to our scientific community by yourstudy?What is the most important personality for scientific research?Ready to accept challenge, persist and never give up.What are your hobbies? What's your favorite book(s)?I like travel since I can feel different culture and learn many different ideas in the travelling. I prefer history books since I can “earn” much valuable experience in the reading.How do you keep balance between research and family?Working effectively in weekday and relaxing completely in weekend.Who influences you mostly in your life?The group of my friends and colleagues. I learn lots to improve myself under their help and criticisms.Could you please give us some advices on improving Chinese Journal of Chemistry?To induce the best chemical research in China, beginning from review papers but finally moving to the top research papers.

Probabilistic Deep Learning Approach to Automate the Interpretation of Multi-phase Diffraction Spectra

Autonomous synthesis and characterization of inorganic materials requires the automatic and accurate analysis of X-ray diffraction spectra. For this task, we designed a probabilistic deep learning algorithm to identify complex multi-phase mixtures. At the core of this algorithm lies an ensemble convolutional neural network trained on simulated diffraction spectra, which are systematically augmented with physics-informed perturbations to account for artifacts that can arise during experimental sample preparation and synthesis. Larger perturbations associated with off-stoichiometry are also captured by supplementing the training set with hypothetical solid solutions. Spectra containing mixtures of materials are analyzed with a newly developed branching algorithm that utilizes the probabilistic nature of the neural network to explore suspected mixtures and identify the set of phases that maximize confidence in the prediction. Our model is benchmarked on simulated and experimentally measured diffraction spectra, showing exceptional performance with accuracies exceeding those given by previously reported methods based on profile matching and deep learning. We envision that the algorithm presented here may be integrated in experimental workflows to facilitate the high-throughput and autonomous discovery of inorganic materials.

Synthesis and Application of Nanolayered and Nanoporous Materials

Nanoscale materials are currently an attractive research subject because their properties are in contrast to their macroscopic counterparts. An inert material, such as bulk platinum metal for example, is known to exhibit a catalytic properties when its size is reduced into nanoscale. A stable material can become flammable or combustible, such as aluminum, and isolator material can become a conductor. Many attractive quantum phenomena also arise from reducing a material size into nanoscale dimensions. This review article discusses the concept, synthesis, and characterization of organic and inorganic nanolayered and nanoporous materials; and their application to catalysis and adsorption processes. Past achievements and future perspectives in the field of nanomaterial researches will be discussed as well. Furthermore, in the era of green chemistry, nanomaterials with all their derivatives are also required to have sustainable characteristics, such as biodegradable and renewable; which emphasizes that the development of nanomaterials in the framework of green chemistry should always be a priority. Through the synthesis of novel and functional nanomaterials using natural and local-based materials around us that are environmentally friendly and relatively easy to be obtained, our goal toward the inheritance of a greener world for the future generations is not an impossible dream.

Metal Sulfide Nanoparticle Synthesis with Ionic Liquids - State of the Art and Future Perspectives.

Metal sulfides are among the most promising materials for a wide variety of technologically relevant applications ranging from energy to environment and beyond. Incidentally, ionic liquids (ILs) have been among the top research subjects for the same applications and also for inorganic materials synthesis. As a result, the exploitation of the peculiar properties of ILs for metal sulfide synthesis could provide attractive new avenues for the generation of new, highly specific metal sulfides for numerous applications. This article therefore describes current developments in metal sulfide nanoparticle synthesis as exemplified by a number of highlight examples. Moreover, the article demonstrates how ILs have been used in metal sulfide synthesis and discusses the benefits of using ILs over more traditional approaches. Finally, the article demonstrates some technological challenges and how ILs could be used to further advance the production and specific property engineering of metal sulfide nanomaterials, again based on a number of selected examples.

Toward autonomous design and synthesis of novel inorganic materials.

Autonomous experimentation driven by artificial intelligence (AI) provides an exciting opportunity to revolutionize inorganic materials discovery and development. Herein, we review recent progress in the design of self-driving laboratories, including robotics to automate materials synthesis and characterization, in conjunction with AI to interpret experimental outcomes and propose new experimental procedures. We focus on efforts to automate inorganic synthesis through solution-based routes, solid-state reactions, and thin film deposition. In each case, connections are made to relevant work in organic chemistry, where automation is more common. Characterization techniques are primarily discussed in the context of phase identification, as this task is critical to understand what products have formed during synthesis. The application of deep learning to analyze multivariate characterization data and perform phase identification is examined. To achieve "closed-loop" materials synthesis and design, we further provide a detailed overview of optimization algorithms that use active learning to rationally guide experimental iterations. Finally, we highlight several key opportunities and challenges for the future development of self-driving inorganic materials synthesis platforms.

Rapid collagen-directed mineralization of calcium fluoride nanocrystals with periodically patterned nanostructures.

Collagen fibrils present periodic structures, which provide space for intrafibrillar growth of oriented hydroxyapatite nanocrystals in bone and contribute to the good mechanical properties of bone. However, there are not many reports focused on bioprocess-inspired synthesis of non-native inorganic materials inside collagen fibrils and detailed forming processes of crystals inside collagen fibrils remain poorly understood. Herein, the rapid intrafibrillar mineralization of calcium fluoride nanocrystals with a periodically patterned nanostructure is demonstrated. The negatively charged calcium fluoride precursor phase infiltrates collagen fibrils through the gap zones creating an intricate periodic mineralization pattern. Later, the nanocrystals initially filling the gap zones only expand gradually into the remaining space within the collagen fibrils. Mineralized tendons with organized calcium fluoride nanocrystals acquire mechanical properties (indentation elastic modulus ∼25.1 GPa and hardness ∼1.5 GPa) comparable or even superior to those of native human dentin and lamellar bone. Understanding the mineral growth processes in collagen may facilitate the development of tissue engineering and repairing.

PHOTO-CATALYSIS PROCESSES IN NON-REGULAR MEDIA

Technologies that cause the least harm to nature from global warming standpoint are becoming called-for. In this regard, photo-catalysis which uses the solar energy for chemical transformations of substances is of great interest for studying possible mechanisms of such processes. At the same time, the use of photo-catalysis significantly expands capabilities of the synthesis of new organic and inorganic materials. Charge phototransfer is always at the heart of photochemical transformations. Such processes can be considered from the point of view of quantum mechanics, and the probability of various mechanisms of the passing processes can be calculated using the apparatus of Green's functions. Analytical expressions for kinetic parameters of the charge transfer process between polyatomic particles in non-regular condensed medium and expressions for the extinction coefficient for appropriate processes of charge photo-transfer are obtained. Based on the analysis of obtained analytical expressions of dark and optical charge transfer processes, correlations between kinetic parameters of these processes are obtained. A methodology for determining kinetic parameters of the charge photo-transfer process on the basis of the shape of light absorption curve by means of the system functioning as the frequency of absorbed photons in various systems is presented. In this respect the general methodology has been applied to various specific processes. A methodology for determining the kinetic parameters of the charge phototransfer process from the shape of the light absorption curve by the system as a function of the frequency of absorbed photons in various systems is presented. The general methodology presented has been applied to various specific processes.

A new class of upconversion luminescence tuning materials based on non-photochromic reaction: Er3+-activated Ba0.7Sr0.3Nb2O6 ferroelectrics

The upconversion (UC) luminescence tuning of phosphors has attracted increasing interest as optical switches, optical sensing, and high-density optical data storage devices. However, the design and synthesis of photo-switchable inorganic luminescent materials were still at primary stage. In this work, a new type of UC luminescence regulation materials, Er3+-activated tetragonal tungsten bronze Ba0.7Sr0.3Nb2O6 ferroelectrics, showing strong susceptibility to visible light irradiation, was reported based on non-photochromic (N-PC) effect. Under visible light irradiation, the maximum luminescent modulation ability reached up to 79.4%. The tuning of UC luminescence was disclosed to tightly rely on the irradiation time and thermal treatment processes. Meanwhile, excellent reproducibility was also demonstrated. Besides, the luminescent readout almost had no any influence on the UC emission, indicating the extremely low destruction to the stored luminescent states. The mechanisms related to the UC luminescence and manipulation were also discussed. In contrast to the previous tuning way based on PC reaction, it is believed that this work shed new light for the understanding of UC modulation fundamentals.

Programming Amphiphilic Peptoid Oligomers for Hierarchical Assembly and Inorganic Crystallization.

Natural organisms make a wide variety of exquisitely complex, nano-, micro-, and macroscale structured materials in an energy-efficient and highly reproducible manner. During these processes, the information-carrying biomolecules (e.g., proteins, peptides, and carbohydrates) enable (1) hierarchical organization to assemble scaffold materials and execute high-level functions and (2) exquisite control over inorganic materials synthesis, generating biominerals whose properties are optimized for their functions. Inspired by nature, significant efforts have been devoted to developing functional materials that can rival those natural molecules by mimicking in vivo functions using engineered proteins, peptides, DNAs, sequence-defined synthetic molecules (e.g., peptoids), and other biomimetic polymers. Among them, peptoids, a new type of synthetic mimetics of peptides and proteins, have received particular attention because they combine the merits of both synthetic polymers (e.g., high chemical stability and efficient synthesis) and biomolecules (e.g., sequence programmability and biocompatibility). The lack of both chirality and hydrogen bonds in their backbone results in a highly designable peptoid-based system with reduced structural complexity and side chain-chemistry-dominated properties.In this Account, we present our recent efforts in this field by programming amphiphilic peptoid sequences for (1) the controlled self-assembly into different hierarchically structured nanomaterials with favorable properties and (2) manipulating inorganic (nano)crystal nucleation, growth, and assembly into superstructures. First, we designed a series of amphiphilic peptoids with controlled side chain chemistries that self-assembled into 1D highly stiff and dynamic nanotubes, 2D membrane-mimetic nanosheets, hexagonally patterned nanoribbons, and 3D nanoflowers. These crystalline nanostructures exhibited sequence-dependent properties and showed promise for different applications. The corresponding peptoid self-assembly pathways and mechanisms were also investigated by leveraging in situ atomic force microscopy studies and molecular dynamics simulations, which showed precise sequence dependency. Second, inspired by peptide- and protein-controlled formation of hierarchical inorganic nanostructures in nature, we developed peptoid-based biomimetic approaches for controlled synthesis of inorganic materials (e.g., noble metals and calcite), in which we took advantage of the substantial side chain chemistry of peptoids and investigated the relationship between the peptoid sequences and the morphology and growth kinetics of inorganic materials. For example, to overcome the challenges (e.g., complexity of protein- and peptide-folding, poor thermal and chemical stabilities) facing the area of protein- and peptide-controlled synthesis of inorganic materials, we recently reported the design of sequence-defined peptoids for controlled synthesis of highly branched plasmonic gold particles. Moreover, we developed a rule of thumb for designing peptoids that predictively enabled the morphological evolution from spherical to coral-shaped gold nanoparticles (NPs). With this Account, we hope to stimulate the research interest of chemists and materials scientists and promote the predictive synthesis of functional and robust materials through the design of sequence-defined synthetic molecules.

Machine learning-guided synthesis of advanced inorganic materials

Synthesis of materials with minimum number of trials is of paramount importance towards the acceleration of advanced materials development. The enormous complexity involved in existing multi-variable synthesis methods leads to high uncertainty, numerous trials and exorbitant cost. Recently, machine learning (ML) has demonstrated tremendous potential for material discovery and property enhancement. Here, we extend the application of ML to guide material synthesis process through the establishment of the methodology including model construction, optimization, and progressive adaptive model (PAM). Two representative multi-variable systems are studied. A classification ML model on chemical vapor grown MoS2 is developed, capable of optimizing the synthesis conditions to achieve a higher success rate. And a regression model is constructed on the hydrothermal-grown carbon quantum dots, to enhance the process-related properties such as the photoluminescence quantum yield. The importance of synthesis parameters on experimental outcomes is particularly extracted from the constructed ML models. Furthermore, off-line analysis shows that enhancement of the experimental outcome with minimized number of trials can be achieved with the effective feedback loops in PAM, suggesting the great potential of involving ML to guide new material synthesis at the beginning stage. This work serves as a proof of concept for using ML in facilitating the synthesis of inorganic materials, thereby revealing the feasibility and remarkable capability of ML in opening up a new promising window for accelerating material development.

Reactivity of Ionic Liquids: Studies on Thermal Decomposition Behavior of 1-Butyl-3-methylimidazolium Tetrafluoroborate

The Ionic Liquid 1-butyl-3-methylimidazolium tetrafluoroborate [C4C1im]BF4 serves as a commonly solvent in inorganic material synthesis and analytics. Nevertheless, its application is frequently associated with trial and error approaches. Thereupon, detailed knowledge on the thermal behavior is the key information for understanding the reactivity of [C4C1im]BF4. 1-butyl-3-methylimidazolium tetrafluoroborate behaves as a glass in the cold, its glass transition temperature being ϑg = −83 °C. During heating with 10 K·min−1 [C4C1im]BF4 appears to be stable above 350 °C with onset temperatures ϑonset, DSC = 375 °C, ϑonset, DTG = 422 °C, and ϑonset, TG = 437 °C. Thereby, thermal decomposition occurs in a single step reaction forming 1-methyl-1H-imidazole (CH3C3H3N2 or C4H6N2), but-1-ene (C4H8), fluoromethane (CH3F) and boron trifluoride (BF3) as main species, as determined by thermogravimetry coupled with mass spectrometry and FTIR spectroscopy. To be more specific in thermal behavior, the temperature and time dependent stability is evaluated here on the basis of the kinetic model of maximum operation temperature − MOT. Clearly, thermal stability rises with application time, thus being 193 °C for one hour, while reaching only 141 °C for one day, and 114 °C for one week. The incipient decomposition (≤ 1 %) at the calculated time dependent maximum operation temperature finally is verified by optical analysis, infrared (IR), and nuclear magnetic resonance (NMR) spectroscopy.