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Correction for ‘Cost-effective carbon fiber precursor selections of polyacrylonitrile-derived blend polymers: carbonization chemistry and structural characterizations’ by Qian Mao et al. , Nanoscale , 2022, 14 , 6357–6372, https://doi.org/10.1039/D2NR00203E.
Thiol containing molecules as both interfacial surface ligands and additives are promising modulators for enhancing photoluminescence (PL) properties, stability, and photovoltaic (PV) performance of metal halide perovskites. However, alkanethiols are much more effective for improving photoluminescence (PL) intensity and stability in metal halide perovskite nanocrystals than in their thin film analogues. Herein, we investigate how additional functional groups on a pyrimidine core can alter thiol reactivity and influence the PL, stability, and PV performance of organic metal halide perovskites. Through an investigation of five different pyrimidine derivatives, it is shown that all derivatives containing thiol groups form thiolates in the presence of the perovskite precursors and increase the photoluminescence intensity of the perovskite film. The largest all-around improvement to the PL intensity, stability, and photovoltaic performance of Cs 0.15 FA 0.85 PbI 3 perovskites is realized through the addition of a hydroxyl group combined with a trifluoromethyl group to form 4-hydroxy-6-(trifluoromethyl)pyrimidine-2-thiol. Furthermore, this investigation helps illuminate how combinations of functional groups can be employed to further increase the beneficial effects over monofunctional additives in organic metal halide perovskites.
Acid-base bifunctional catalysts play a crucial role in converting high-free fatty acid (FFA) feedstocks into biodiesel by enabling the simultaneous esterification and transesterification of triglycerides in a single step, thereby minimizing saponification and streamlining the process. In this study, we report the design and development of a novel N-doped acid-base bifunctional biochar catalyst synthesized from renewable biomass precursors- glucose and chitosan. The catalyst’s acidic sites were introduced via surface functionalization with o-sulfobenzoic acid cyclic anhydride, grafting -SO₃H groups onto the carbon framework, while basic sites were generated from amine functionalities (-NH) derived from chitosan, yielding a robust and truly bifunctional surface. The catalyst was characterized and used for the microwave-assisted transesterification of waste cooking oil, and process optimization using response surface methodology (RSM-CCD) yielding a maximum biodiesel yield of 98.8 ± 0.4% under optimal conditions (methanol-to-oil molar ratio 20:1, catalyst loading 5.7 wt%, temperature 99 °C, and reaction time 46.6 min). The catalyst demonstrated good stability, maintaining a yield of 92.2 ± 0.4% after eight reuse cycles. A Life Cycle Assessment (LCA) conducted for 1 kg of biodiesel production revealed a global warming potential of 0.85 kg CO 2 eq and human toxicity potential of 1.59 kg 1,4-DB eq, with the largest environmental contributions arising from catalyst preparation and reuse. In conclusion, this work highlights a green and circular approach to biodiesel production, combining renewable catalyst design, waste feedstock utilization, and quantitative sustainability assessment to guide future developments in sustainable catalysis and biofuel engineering.
Advances in genome engineering have improved our ability to perturb microbial metabolic networks, yet bioproduction campaigns often struggle with parsing complex metabolic datasets to efficiently enhance product titers. We address this challenge by coupling laboratory automation with machine learning to systematically optimize the production of isoprenol, a sustainable aviation fuel precursor, in Pseudomonas putida. The simultaneous downregulation through CRISPR interference of combinations of up to four gene targets, guided by machine learning, permitted us to increase isoprenol titer 5-fold in six consecutive design-build-test-learn cycles. Moreover, machine learning enabled us to swiftly explore a vast experimental design space of 800,000 possible combinations by strategically recommending approximately 400 priority constructs. High-throughput proteomics allowed us to validate CRISPRi downregulation and identify biological mechanisms driving production increases. Our work demonstrates that ML-driven automated design-build-test-learn cycles, when combined with rigorous data validation, can rapidly enhance titers without specific biological knowledge, suggesting that it can be applied to any host, product, or pathway.
Engineered microorganisms have the potential to convert renewable substrates into biofuels and valuable bioproducts, which offers an environmentally sustainable alternative to fossil-fuel-derived products. Isoprenoids are a diverse class of biologically derived compounds that have commercial applications as various commodity chemicals, including biofuels and biofuel precursor molecules.
Using a combination of in-situ high-resolution digital image correlation (HR-DIC), Heaviside-DIC method (H-DIC), and crystal plasticity finite element (CPFE), we investigate the evolution of intragranular lattice rotations and slip activity during monotonic and cyclic loading in a high performance, polycrystalline face centered cubic material. The CPFE employs a quasi-3D model microstructure, which is a highly resolved mirror representation of the experimental in-situ test sample. In agreement, the measurements and calculations reveal that most grains, regardless of their size and lattice orientation, develop intragranular lattice rotation gradients that span the grain. For a small cluster of grains on the deformed material, we perform HR-DIC analysis of slip lines to demonstrate agreement in the active slip systems and changes in this local slip activity across the individual grains. The combined analysis reveals that deforming grains are divided into sub-granular regions of uniform lattice rotation and these regions are most often associated with only one or two active slip systems. The gradient lines that divide them correspond to changes in the predominant slip system. The model is used to examine the evolution of intragranular lattice rotation in a single fully reversed tension-compression cycle. The calculations indicate that intragranular gradients intensify during the reverse loading path as nearest neighboring regions appear to shed lattice rotation, increasing the lattice rotation in some regions, while shutting down rotation in neighboring regions. So these findings provide insight into the irreversible changes that develop within deforming grains at the scale of the grain, particularly the heterogeneous development of intragranular lattice rotation in early stages of deformation, which could serve as precursors to localization.
The Biological Upgrading of Sugars (BUS) project directly targets the anaerobic conversion of lignocellulosic feedstocks into intermediate molecules readily upgradeable to fuel precursors. Recent efforts on the BUS project have a particular emphasis on the biological production of butyric acid, an intermediate that can be readily upgraded to sustainable aviation fuel, diesel blend-stocks, and high value chemicals. The BUS project approaches this direction through a combination of strain engineering, fermentation process engineering, development of novel separations technologies, and the design and build of pilot scale systems. Our ultimate project goal is to develop an integrated cost-effective process at pilot scale to achieve DOE's MYPP targets of $2.50/GGE. The major thrust of the BUS project over the last project cycle was on the development of integrated processes surrounding the anaerobic production of carboxylic acids using diverse Clostridium species. We developed and expanded genetic tools for several Clostridium species and rewired microbial metabolism in an attempt to maximize substrate utilization and flux towards butyric acid. We designed and built novel bioreactors with an in situ product recovery system enabling the biological production and recovery of highly purified acids. We leveraged this system to generate 100s of grams of acid from corn stover hydrolysate. In this presentation we highlight data surrounding our proposed process and accompanying results from technoeconomic and life-cycle analyses of our integrated process. Finally, we detail plans of our pilot scale reactor system that is in process and discuss our future routes towards achieving economically viable and sustainable diesel and jet blendstocks.
Porous metal oxide–metal-organic framework (MO x @MOF) hybrids offer synergistic effects that enhance surface charge density, electronic structure, and textural properties, making them ideal for self-powered sensing applications. Here, uniform, and pinhole-free ternary porous ZnO–PTFE@ZIF-8 hybrid films are developed on room-temperature co-sputtered ZnO–polytetrafluoroethylene (PTFE) composite films, where ZnO serves as a self-sacrificial precursor to precisely regulate ZIF-8 (Zn-MeIm 2 ) growth through solvothermal methods. The resulting TENG achieves a high output power density of 0.67 mW cm −2 , attributed to the synergistic effects of fluorine-rich PTFE and methyl-functionalized ZIF-8, which enhance surface charge density and dielectric response. By tuning PTFE content in the ZnO–PTFE composite, the dielectric constant and triboelectric output is optimized. The ZP60@ZIF-8-based device also demonstrates excellent humidity sensing performance, with a wide detection range (20–99% RH) and ultrahigh sensitivity (R V % of 19 900%, R I % of 19 325% at 99% RH). These results position ZP@ZIF-8-based TENGs as promising platforms for next-generation self-powered sensors and smart wearable electronics.
The effective operation of atomic layer deposition (ALD) feeding system is the premise of realizing specific ALD processes. In the present work, a detailed computational fluid dynamics (CFD) model of the feeding system has been developed and validated, which accounts for the roles of ALD valves and manifolds. A numerical simulation of the compressible fluid flow and heat/mass transfer within the feeding system was conducted. The dosing amounts and the spatiotemporal distributions of the precursors can be accurately predicted using the CFD model, as validated by experimental results. Different precursors, operating conditions, and structures of the feeding system were simulated and analyzed to examine the operating flexibility of the feeding system. The simulation results can be adopted as the upstream boundary conditions for simulations of the ALD process in the reaction chamber. The substrate-scale simulation indicates that the effect of the feeding system on the film deposition is highly related to the surface kinetics of ALD. The present work can serve as a guide for the development and optimization of different ALD-based processes via proper operation and even the design of the feeding system.
We show that the reflection interference fringe (RIF) is formed on a screen far away from the microdroplets placed on a prism-based substrate, which have low contact angles and thin droplet heights, caused by the dual convex–concave profile of the droplet, not a pure convex profile. The geometric formulation shows that the interference fringes are caused by the optical path difference when the reflected rays from the upper convex profile at the droplet–air interface interfere with reflection from the lower concave profile at oblique angles lower than the critical angle. Analytic solutions are obtained for the droplet height and the contact angle out of the fringe number and the fringe radius in RIF from the geometric formulation. Furthermore, the ray tracing simulation is conducted using the custom-designed code. The geometric formulation and the ray tracing show excellent agreement with the experimental observation in the relation between the droplet height and the fringe number and the relation between the contact angle and the fringe radius. This study is remarkable as the droplet's dual profile cannot be easily observed with the existing techniques. However, the RIF technique can effectively verify the existence of a dual profile of the microdroplets in a simple setup. In this work, the RIF technique is successfully developed as a new optical diagnostic technique to determine the microdroplet features, such as the dual profile, the height, the contact angle, the inflection point, and the precursor film thickness, by simply measuring the RIF patterns on the far-field screen.
Converting high-performing powder catalysts from the laboratory reactor scale into effective extruded catalysts at the industrial scale remains a hurdle for advancing sustainable catalytic processes, such as the conversion of biogenic syngas into high octane gasoline. Recently, a process-intensified syngas-to-hydrocarbons (STH) reaction in a single reactor under relatively mild conditions (220–250 ºC, 0.75–2.0 MPa) was reported, enabled by the development of a dimethyl ether (DME) homologation catalyst, Cu-modified H-BEA (Cu/BEA) zeolite. In this study, we explore approaches for synthesizing engineered Cu/BEA catalysts for use in the STH reaction to retain the high performance observed with the powder catalyst. We demonstrate that changes to the order of manufacturing steps (i.e., Cu deposition, alumina binder addition, and extrusion) result in observable changes to key active sites (Brønsted acid sites and zeolitic Cu + species), and ultimately, catalyst performance. When the Cu precursor was added directly to BEA before extrusion, both types of active sites were stabilized, preserving the activity of the powder catalyst. However, when the Cu precursor was added after extrusion, the resulting Cu species were mobile, destabilizing Brønsted acid sites and leading to near-zero activity.
In this study, we investigated the synthesis of copper selenide nanoplatelets (NPLs) through a cation exchange reaction (CER) in 5-monolayer-thick CdSe NPLs using Cu(I) and Cu(II) precursors. We discovered that the exposure of CdSe NPLs to a Cu(I) precursor led to the transformation of NPLs into Cu 2-x Se while maintaining their nanoplatelet morphology. The replacement of Cd(II) with Cu(I) prevailed over the formation of doped structures. In the case of the Cu(II) precursor, we observed that Cu(II) was first reduced to Cu(I) before being intercalated into the host lattice, resulting in the synthesis of Cu 2-x Se, similar to CER with Cu(I) precursors but without preservation of the initial morphology of NPLs. Interestingly, the presence of oxygen was found to facilitate the cation exchange processes in CdSe NPLs, whereas a nitrogen atmosphere suppressed the CER. Further, despite the similar ionic sizes of Cu(I) and Cu(II), the substitution of Cd(II) with Cu(II) was found to be challenging, possibly due to the involvement of redox processes resulting in the significant deterioration of initial CdSe NPLs. We demonstrate that CER can achieve near-complete substitution of cadmium atoms with monovalent copper at room temperature. Understanding the processes involved in CERs is crucial for engineering more complex structures, such as high-entropy nanoparticles involving cation exchange with different oxidation states and development of material synthesis using machine learning and artificial intelligence approaches.
Increasing adoption of downsized, boosted, spark-ignition engines has improved vehicle fuel economy, and continued improvement is desirable to reduce carbon emissions in the near-term. However, this strategy is limited by damaging preignition events which can cause hardware failure. Research to date has shed light on various contributing factors related to fuel and lubricant properties as well as calibration strategies, but the causal factors behind an individual preignition cycle remain elusive. If actionable precursors could be identified, mitigation through active control strategies would be possible. This paper uses artificial neural networks to search for identifiable precursors in the cylinder pressure data from a large real-world data set containing many preignition cycles. It is found that while follow-up preignition cycles in clusters can be readily predicted, the initial preignition cycle is not predictable based on features of the cylinder pressure. Further, this indicates that the alternating pattern of preignition cycles within clusters is influenced by the thermodynamic state as reflected in the pressure, but that the trigger for the initial preignition cycle is not thermodynamic in nature, but more likely tied to a critical threshold in the chemistry of the fuel/lubricant mixture in the upper crevice or other factors related to the presence of an ignition source.
Recently, the integration of electronic elements with cellular scaffolds has brought forth the ability to monitor and control tissue function actively by using flexible free-standing two-dimensional (2D) systems. Capabilities for electrically probing complex, physicochemical and biological three-dimensional (3D) microenvironments demand, however, 3D electronic scaffolds with well-controlled geometries and functional-component distributions. This work presents the development of flexible 3D electronic scaffolds with precisely defined dimensions and microelectrode configurations formed using a process that relies on geometric transformation of 2D precursors by compressive buckling. It demonstrates a capability to fabricate these constructs in diverse 3D architectures and/or electrode distributions aimed at achieving an enhanced level of control and regulation of tissue function relatively to that of other approaches. In addition, this work presents the integration of these 3D electronic scaffolds within engineered 3D cardiac tissues, for monitoring of tissue function, controlling tissue contraction through electrical stimulation, and initiating on-demand, local release of drugs, each through well-defined volumetric spaces. These ideas provide opportunities in fields ranging from in vitro drug development to in vivo tissue repair and many others.
To meet the increasing demand for graphitizable carbon products, such as needle coke and carbon fiber, more carbon feedstocks capable of forming anisotropy should be utilized. Non-coking coals are widely available but are not typically suitable for producing anisotropic carbons due to lacking proper coal chemistry. This work used secondary gas-phase reactions (SGR) during coal pyrolysis to improve the coal tar chemistry of a non-coking coal for anisotropic carbon production. SGR pyrolysis temperatures and residence times were varied (T = 800–900°C and τ = 0–2.5 s), and analysis of the intermediate coal tar products showed that as these SGR pyrolysis conditions increased, the oxygen and aliphatic concentrations decreased, whereas aromatic contents and molecular weights increased. Without any SGR, microscopy of the thermally-treated coal tar pitch product revealed that the coal tar pitch was isotropic; however, upon using increased SGR pyrolysis conditions, the resulting coal tar pitch samples substantially increased in the percentage and quality of anisotropy formation. Further, the products' analyses show clear trends of modified chemical properties in the intermediate coal tar and improved anisotropy results. Thus, the results presented in this work show that by controlling the SGR during pyrolysis of a non-coking coal, this approach can modify the coal tar chemistry towards a precursor more suitable for quality anisotropic carbon material production.
Biological approaches show promise for the sustainable and cost competitive production of commodity fuels and chemicals. A lot of efforts have been devoted to engineering microbial chassis to produce select fuels and chemicals. These approaches have had some level of success exemplified, of course, by the production of ethanol at high yield and titer but also recent successes with commodity chemicals such as 1,4-butanediol, 1,3-propanediol, and even to some extent with sustainable aviation fuel intermediates such as farnesene. However, many of these processes still suffer from low yields, usually below the standard needed to drive a sustainable and atom efficient bioeconomy. Additionally, for many other chemicals and fuel precursors, titers and yields are only a fraction of what they are for ethanol. Indeed, there exist many limiting factors associated with the use of microbial biocatalysts. Some of these factors include the diversion of carbon from products to sustain growth and biomass formation, the production of byproducts or regulatory mechanisms, the toxicity of end products or intermediates, and the difficulty of separating products from growth media.