Chemical and Biomolecular Engineering Publications

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The role of hydrogen in the energy transition of the oil and gas industry
(Elsevier, 2024) Zhang, Kai; He, Liu; Jiang, Liangliang; Jiang, Shu; Yu, Ruyang; Lau, Hon Chung; Xie, Congjiao; Chen, Zhangxin
Hydrogen, primarily produced from steam methane reforming, plays a crucial role in oil refining, and provides a solution for the oil and gas industry's long-term energy transition by reducing CO2 emissions. This paper examines hydrogen’s role in this transition. Firstly, experiences from oil and gas exploration, including in-situ gasification, can be leveraged for hydrogen production from subsurface natural hydrogen reservoirs. The produced hydrogen can serve as fuel for generating steam and heat for thermal oil recovery. Secondly, hydrogen can be blended into gas for pipeline transportation and used as an alternative fuel for oil and gas hauling trucks. Additionally, hydrogen can be stored underground in depleted gas fields. Lastly, oilfield water can be utilized for hydrogen production using geothermal energy from subsurface oil and gas fields. Scaling up hydrogen production faces challenges, such as shared use of oil and gas infrastructures, increased carbon tax for promoting blue hydrogen, and the introduction of financial incentives for hydrogen production and consumption, hydrogen leakage prevention and detection.
Aligned colloidal clusters in an alternating rotating magnetic field elucidated by magnetic relaxation
(National Academy of Sciences, 2024) Spatafora-Salazar, Aldo; Lobmeyer, Dana M.; Cunha, Lucas H. P.; Joshi, Kedar; Biswal, Sibani Lisa
Precise control at the colloidal scale is one of the most promising bottom–up approaches to fabricating new materials and devices with tunable and precisely engineered properties. Magnetically driven colloidal assembly offers great versatility because of the ability to externally tune particle–particle interactions and to construct a host of particle arrangements. However, despite previous efforts to probe the parameter space, global orientational control in conjunction with two-dimensional microstructural control has remained out of reach. Furthermore, the magnetic relaxation time of superparamagnetic beads has been largely overlooked despite being a key feature of the magnetic response. Here, we take advantage of the magnetic relaxation time of superparamagnetic beads in an alternating rotating magnetic field and show how harnessing this feature facilitates the formation of oriented clusters. The orientation of these clusters can be controlled by field parameters. Using experiments, simulations, and theory, we probe a two-particle system (dimer) under this alternating rotating magnetic field and use its dynamics to provide insights into the collective response that forms clusters. We find that the type of field has significant implications for the dipolar interactions between the colloids because of the nonnegligible magnetic relaxation. Moreover, we find that the competing time scales of the magnetic relaxation and the alternating field generate an anisotropic interaction potential that drives cluster alignment. By exploiting the magnetic relaxation time of magnetic systems, we can tailor new types of interparticle interactions, thereby expanding the capabilities of colloidal assembly in engineering unique materials and devices.
Revealing the impact of ammonium ions from different low-dimensional perovskite structures on the film formation and degradation mechanism of FAPbI3 via sequential deposition
(AIP Publishing LLC, 2024) Wang, Yafei; Yuan, Shihao; Feng, Rongsen; Diao, Zecheng; Huang, Jie; Liao, Jiacai; Sidhik, Siraj; Shuai, Xinting; Wang, Meicong; Zou, Tao; Liang, Zhongwei; Zhang, Ting; Mohite, Aditya D.; Li, Shibin
In recent years, the organic–inorganic hybrid perovskite community has been widely employed as the photo-active layer in optical-electronic devices. The black α-phase formamidinium lead iodide (FAPbI3) is the most popular perovskite for realizing high-efficiency solar cells due to its suitable bandgap. However, the issue of stability is also a concern in the research on FAPbI3 solar cells. In this study, different ammonium ions, such as butylamine (BA), guanidine (GA), and butylene diamine (BDA), which are commonly used to construct two-dimensional perovskites, including Ruddlesden–Popper, Dion–Jacobson, and alternating cations in the interlayer space, respectively, were introduced in the fabrication of FAPbI3 using a sequential deposition method. Several structures of PbI2 precursor films were formed by introducing the aforementioned ions, which exhibited different arrangements and connection modes in lead iodides. BA-PbI2 precursor films exhibited higher specific surface areas, which were beneficial to the diffusion, ion exchange, and sequential reaction of FA+. The BDA-PbI2 precursor film slowed down the sequential reaction of FAPbI3 because of reduced van der Waals bonds. The nucleation dynamics and degradation processes of perovskites were deeply investigated in this study. Solar cells based on BA-PbI2, GA-PbI2, and BDA-PbI2 were also fabricated.
Emergence of microplastics in African environmental drinking water sources: A review on sources, analysis and treatment strategies
(Elsevier, 2024) Adewuyi, Adewale; Li, Qilin; NSF Nanosystems Engineering Research Center for Nanotechnology-Enabled Water Treatment
The emergence of microplastics (MPs) as microcontaminants in environmental drinking water sources is a problem in Africa that requires immediate action. Therefore, this review focused on understanding the sources of MPs in African water systems, treatment strategies, analytical methods for identification and quantification, and Africa's pollution index. From the findings, the source of MPs in African water systems was attributed to unregulated importation of plastic products, poor waste management, lack of awareness, poor environmental value system and the inability of local polymer industries to adjust to new policies on plastic management. Most studies identified microfibers and microbeads to be the primary sources of plastics that break down to MPs in African drinking water sources, with polystyrene (PS), polypropylene (PP), and polyethylene (PE) being frequently detected. Current methods for identification, and quantification of MPs in most studies conducted in Africa were not developed in Africa but was adopted from developed countries and, in some cases, modified to meet specific analytical requirements. More studies are necessary for in-depth understanding of the fate and pollution index of MP in African environmental water systems. Furthermore, the interaction between MP and other pollutants in the water system still needs to be better understood. This review suggests membrane and rapid sand filtration methods as promising methods that may be considered for removing MPs from water systems in Africa.
Closing PFAS analytical gaps: Inter-method evaluation of total organofluorine techniques for AFFF-impacted water
(Elsevier, 2024) Dixit, Fuhar; Antell, Edmund H.; Faber, Katharine A.; Zhang, Chuhui; Pannu, Manmeet W.; Plumlee, Megan H.; Van Buren, Jean; Doroshow, Abraham; Pomerantz, William C. K.; Arnold, William A.; Higgins, Christopher P.; Peaslee, Graham F.; Alvarez-Cohen, Lisa; Sedlak, David L.; Ateia, Mohamed
Multiple poly- and perfluoroalkyl substances (PFASs) are present in aqueous film-forming foams (AFFF) used for firefighting activities. Currently, no single analytical technique provides a complete accounting of total PFASs or total organofluorine content in AFFF-contaminated samples. To provide insight into the performance of existing methods, we compared ten previously described PFAS measurement techniques. In AFFF-amended tap water, US EPA Methods 533 and 1633, adsorbable organic fluorine with particle induced gamma emission spectroscopy (AOF-PIGE) and fluorine-19 nuclear magnetic resonance (19F NMR) provided similar estimates of total fluorine. The total oxidizable precursor (TOP) assay, suspect screening, and adsorbable organic fluorine with combustion ion chromatography (AOF-CIC) yielded estimates of total organic fluorine that were about two to three times higher than the other techniques. Proximate to AFFF sources, suspect screening and modified EPA Method 1633 yielded higher results, while the TOP assay results were between the other two sets of analyses. Further from sources, suspect screening, modified EPA Method 1633, and the TOP assay yielded similar results that were 4-fold higher than results from targeted quantification methods, such as EPA Method 1633. These results are consistent with expectations about PFAS behavior and inform the selection of analytical techniques used for PFAS contamination characterization efforts.
Emergency of per- and polyfluoroalkyl substances in drinking water: Status, regulation, and mitigation strategies in developing countries
(Elsevier, 2024) Adewuyi, Adewale; Li, Qilin; NSF Nanosystems Engineering Research Center for Nanotechnology-Enabled Water Treatment
The detection of per- and polyfluoroalkyl substances (PFAS) in water presents a significant challenge for developing countries, requiring urgent attention. This review focuses on understanding the emergence of PFAS in drinking water, health concerns, and removal strategies for PFAS in water systems in developing countries. This review indicates the need for more studies to be conducted in many developing nations due to limited information on the environmental status and fate of PFAS. The health consequences of PFAS in water are enormous and cannot be overemphasized. Efforts are ongoing to legislate a national standard for PFAS in drinking water. Currently, there are few known mitigation efforts from African countries, in contrast to several developing nations in Asia. Therefore, there is an urgent need to develop economically viable techniques that could be integrated into large-scale operations to remove PFAS from water systems in the region. However, despite the success achieved with removing long-chain PFAS from water, more studies are required on strategies for eliminating short-chain moieties in water.
PFAS occurrence and distribution in yard waste compost indicate potential volatile loss, downward migration, and transformation
(Royal Society of Chemistry, 2024) Saha, Biraj; Ateia, Mohamed; Fernando, Sujan; Xu, Jiale; DeSutter, Thomas; Iskander, Syeed Md
We discovered high concentrations of PFAS (18.53 ± 1.5 μg kg−1) in yard waste compost, a compost type widely acceptable to the public. Seventeen out of forty targeted PFAS, belonging to six PFAS classes were detected in yard waste compost, with PFCAs (13.51 ± 0.99 μg kg−1) and PFSAs (4.13 ± 0.19 μg kg−1) being the dominant classes, comprising approximately 72.5% and 22.1% of the total measured PFAS. Both short-chain PFAS, such as PFBA, PFHxA, and PFBS, and long-chain PFAS, such as PFOA and PFOS, were prevalent in all the tested yard waste compost samples. We also discovered the co-occurrence of PFAS with low-density polyethylene (LDPE) and polyethylene terephthalate (PET) plastics. Total PFAS concentrations in LDPE and PET separated from incoming yard waste were 7.41 ± 0.41 μg kg−1 and 1.35 ± 0.1 μg kg−1, which increased to 8.66 ± 0.81 μg kg−1 in LDPE and 5.44 ± 0.56 μg kg−1 in PET separated from compost. An idle mature compost pile revealed a clear vertical distribution of PFAS, with the total PFAS concentrations at the surface level approximately 58.9–63.2% lower than the 2 ft level. This difference might be attributed to the volatile loss of short-chain PFCAs, PFAS's downward movement with moisture, and aerobic transformations of precursor PFAS at the surface.
Electrothermal mineralization of per- and polyfluoroalkyl substances for soil remediation
(Springer Nature, 2024) Cheng, Yi; Deng, Bing; Scotland, Phelecia; Eddy, Lucas; Hassan, Arman; Wang, Bo; Silva, Karla J.; Li, Bowen; Wyss, Kevin M.; Ucak-Astarlioglu, Mine G.; Chen, Jinhang; Liu, Qiming; Si, Tengda; Xu, Shichen; Gao, Xiaodong; JeBailey, Khalil; Jana, Debadrita; Torres, Mark Albert; Wong, Michael S.; Yakobson, Boris I.; Griggs, Christopher; McCary, Matthew A.; Zhao, Yufeng; Tour, James M.
Per- and polyfluoroalkyl substances (PFAS) are persistent and bioaccumulative pollutants that can easily accumulate in soil, posing a threat to environment and human health. Current PFAS degradation processes often suffer from low efficiency, high energy and water consumption, or lack of generality. Here, we develop a rapid electrothermal mineralization (REM) process to remediate PFAS-contaminated soil. With environmentally compatible biochar as the conductive additive, the soil temperature increases to >1000 °C within seconds by current pulse input, converting PFAS to calcium fluoride with inherent calcium compounds in soil. This process is applicable for remediating various PFAS contaminants in soil, with high removal efficiencies ( >99%) and mineralization ratios ( >90%). While retaining soil particle size, composition, water infiltration rate, and cation exchange capacity, REM facilitates an increase of exchangeable nutrient supply and arthropod survival in soil, rendering it superior to the time-consuming calcination approach that severely degrades soil properties. REM is scaled up to remediate soil at two kilograms per batch and promising for large-scale, on-site soil remediation. Life-cycle assessment and techno-economic analysis demonstrate REM as an environmentally friendly and economic process, with a significant reduction of energy consumption, greenhouse gas emission, water consumption, and operation cost, when compared to existing soil remediation practices.
Challenges in photocatalysis using covalent organic frameworks
(IOP Publishing, 2024) Jiang, Shu-Yan; Senftle, Thomas P.; Verduzco, Rafael; NanoEnabled Water Treatment Center
Photocatalysis is an attractive, energy-efficient technology for organic transformations, polymer synthesis, and degradation of environmental pollutants. There is a need for new photocatalysts stable in different media and that can be tailored for specific applications. Covalent organic frameworks (COF) are crystalline, nanoporous materials with π-conjugated backbone monomers, representing versatile platforms as heterogeneous, metal-free photocatalysts. The backbone structure can be tailored to achieve desired photocatalytic properties, side-chains can mediate adsorption, and the nanoporous structure provides large surface area for molecular adsorption. While these properties make COFs attractive as photocatalysts, several fundamental questions remain regarding mechanisms for different photocatalytic transformations, reactant transport into porous COF structures, and both structural and chemical stability in various environments. In this perspective, we provide a brief overview of COF photocatalysts and identify challenges that should be addressed in future research seeking to employ COFs as photocatalysts. We close with an outlook and perspective on future research directions in the area of COF photocatalysts.
Hydrogen Peroxide Electrosynthesis in a Strong Acidic Environment Using Cationic Surfactants
(American Chemical Society, 2024) Adler, Zachary; Zhang, Xiao; Feng, Guangxia; Shi, Yaping; Zhu, Peng; Xia, Yang; Shan, Xiaonan; Wang, Haotian
The two-electron oxygen reduction reaction (2e–-ORR) can be exploited for green production of hydrogen peroxide (H2O2), but it still suffers from low selectivity in an acidic electrolyte when using non-noble metal catalysts. Here, inspired by biology, we demonstrate a strategy that exploits the micellization of surfactant molecules to promote the H2O2 selectivity of a low-cost carbon black catalyst in strong acid electrolytes. The surfactants near the electrode surface increase the oxygen solubility and transportation, and they provide a shielding effect that displaces protons from the electric double layer (EDL). Compared with the case of a pure acidic electrolyte, we find that, when a small number of surfactant molecules were added to the acid, the H2O2 Faradaic efficiency (FE) was improved from 12% to 95% H2O2 under 200 mA cm–2, suggesting an 8-fold improvement. Our in situ surface enhanced Raman spectroscopy (SERS) and optical microscopy (OM) studies suggest that, while the added surfactant reduces the electrode’s hydrophobicity, its micelle formation could promote the O2 gas transport and its hydrophobic tail could displace local protons under applied negative potentials during catalysis, which are responsible for the improved H2O2 selectivity in strong acids.
Ultra-high capacity, multifunctional nanoscale sorbents for PFOA and PFOS treatment
(Springer Nature, 2023) Lee, Junseok; Kim, Changwoo; Liu, Chen; Wong, Michael S.; Cápiro, Natalie L.; Pennell, Kurt D.; Fortner, John D.
Here, we describe surface functionalized, superparamagnetic iron oxide nanocrystals (IONCs) for ultra-high PFAS sorption and precise, low energy (magnetic) separation, considering perfluorooctanoic acid (PFOA) and perfluorooctanesulfonic acid (PFOS). As a function of surface coating, sorption capacities described are considerably higher than previous studies using activated carbon, polymers, and unmodified metal/metal oxides, among others. In particular, positively charged polyethyleneimine (PEI) coated IONCs demonstrate extreme sorption capacities for both PFOA and PFOS due to electrostatic and hydrophobic interactions, along with high polymer grafting densities, while remaining stable in water, thus maintaining available surface area. Further, through a newly developed method using a quart crystal microbalance with dissipation (QCM-D), we present real-time, interfacial observations (e.g., sorption kinetics). Through this method, we explore underpinning mechanism(s) for differential PFAS (PFOA vs PFOS) sorption behavior(s), demonstrating that PFAS functional head group strongly influence molecular orientation on/at the sorbent interface. The effects of water chemistry, including pH, ionic composition of water, and natural organic matter on sorption behavior are also evaluated and along with material (treatment) demonstration via bench-scale column studies.
Engineering chirality at wafer scale with ordered carbon nanotube architectures
(Springer Nature, 2023) Doumani, Jacques; Lou, Minhan; Dewey, Oliver; Hong, Nina; Fan, Jichao; Baydin, Andrey; Zahn, Keshav; Yomogida, Yohei; Yanagi, Kazuhiro; Pasquali, Matteo; Saito, Riichiro; Kono, Junichiro; Gao, Weilu; Carbon Hub; Smalley-Curl Institute
Creating artificial matter with controllable chirality in a simple and scalable manner brings new opportunities to diverse areas. Here we show two such methods based on controlled vacuum filtration - twist stacking and mechanical rotation - for fabricating wafer-scale chiral architectures of ordered carbon nanotubes (CNTs) with tunable and large circular dichroism (CD). By controlling the stacking angle and handedness in the twist-stacking approach, we maximize the CD response and achieve a high deep-ultraviolet ellipticity of 40 ± 1 mdeg nm−1. Our theoretical simulations using the transfer matrix method reproduce the experimentally observed CD spectra and further predict that an optimized film of twist-stacked CNTs can exhibit an ellipticity as high as 150 mdeg nm−1, corresponding to a g factor of 0.22. Furthermore, the mechanical rotation method not only accelerates the fabrication of twisted structures but also produces both chiralities simultaneously in a single sample, in a single run, and in a controllable manner. The created wafer-scale objects represent an alternative type of synthetic chiral matter consisting of ordered quantum wires whose macroscopic properties are governed by nanoscopic electronic signatures and can be used to explore chiral phenomena and develop chiral photonic and optoelectronic devices.
The energetics and evolution of oxidoreductases in deep time
(Wiley, 2024) McGuinness, Kenneth N.; Fehon, Nolan; Feehan, Ryan; Miller, Michelle; Mutter, Andrew C.; Rybak, Laryssa A.; Nam, Justin; AbuSalim, Jenna E.; Atkinson, Joshua T.; Heidari, Hirbod; Losada, Natalie; Kim, J. Dongun; Koder, Ronald L.; Lu, Yi; Silberg, Jonathan J.; Slusky, Joanna S. G.; Falkowski, Paul G.; Nanda, Vikas
The core metabolic reactions of life drive electrons through a class of redox protein enzymes, the oxidoreductases. The energetics of electron flow is determined by the redox potentials of organic and inorganic cofactors as tuned by the protein environment. Understanding how protein structure affects oxidation–reduction energetics is crucial for studying metabolism, creating bioelectronic systems, and tracing the history of biological energy utilization on Earth. We constructed ProtReDox (https://protein-redox-potential.web.app), a manually curated database of experimentally determined redox potentials. With over 500 measurements, we can begin to identify how proteins modulate oxidation–reduction energetics across the tree of life. By mapping redox potentials onto networks of oxidoreductase fold evolution, we can infer the evolution of electron transfer energetics over deep time. ProtReDox is designed to include user-contributed submissions with the intention of making it a valuable resource for researchers in this field.
Niobium Oxide Photocatalytically Oxidizes Ammonia in Water at Ambient Conditions
(SciELO, 2024) Elias, Welman; Clark, Chelsea; Heck, Kimberly; Arredondo, Jacob; Wang, Bo; Toro, Andras; Kürtib, László; Wong, Michael; Nanosystems Engineering Research Center for Nanotechnology-Enabled Water Treatment
Ammonia contamination in water is a significant environmental issue since it is toxic and leads to eutrophication. Photocatalysis has been investigated as a strategy for ammonia degradation but can potentially form toxic nitrite (NO2–) and nitrate (NO3–) byproducts. This work reports on the ability of niobium oxide (Nb2O5) to photocatalytically oxidize aqueous-phase ammonia (NH3). Whereas as-synthesized Nb2O5 showed little catalytic activity (< 1% NH3 conversion after 6 h of UV-C irradiation, at room temperature and atmospheric pressure, and under O2 headspace), Nb2O5 treated in basic solution (OH-Nb2O5) was able to photocatalytically degrade NH3 at ca. 9% conversion after six hours, with ca. 70% selectivity to the desired N2, with a first-order rate constant of ca. 12 times higher than the as synthesize catalyst (1.6 × 10–3 min–1 vs. 2.0 × 10–2 min–1). Raman spectroscopic analysis indicated the presence of terminal Nb=O species after base treatment of Nb2O5, implicating them as catalytically active sites. These results underscore how a simple structural modification can significantly affect photocatalytic activity for aqueous ammonia oxidation.
Complete defluorination of per- and polyfluoroalkyl substances — dream or reality?
(Elsevier, 2023) Arana Juve, Jan-Max; Wang, Bo; Wong, Michael S.; Ateia, Mohammed; Wei, Zongsu; The Catalysis and Nanomaterials Laboratory
The consensus of removing per- and polyfluoroalkyl substances (PFAS) from the environment is widely recognized and enlightened by the near-zero standards released from the U.S. Environmental Protection Agency in 2023. The only way to achieve the goal of zero fluoro-pollution is to fully defluorinate or mineralize PFAS, but current technologies only partially defluorinate a limited number of PFAS, which can lead to the creation of potentially more toxic short-chain intermediates. Therefore, we discuss herein the need to broaden the scope of tested PFAS, summarize the state-of-the-art degradation technologies, and provide perspectives to achieve complete defluorination. Besides fundamental knowledge gaps in defluorination reactions, technological gaps in the aspects of water matrix effects, pilot tests, and cost analysis also limit the application and comparison of different treatment technologies. This work would shed light on further research to find solutions in the complete defluorination of PFAS.
Application of magnetic nanoparticles as demulsifiers for surfactant-enhanced oil recovery
(Wiley, 2023) Zhang, Leilei; Bai, Chutian; Zhang, Zhuqing; Wang, Xinglin; Nguyen, Thao Vy; Vavra, Eric; Puerto, Maura; Hirasaki, George J.; Biswal, Sibani Lisa
Nonionic surfactants are increasingly being applied in oil recovery processes due to their stability and low adsorption onto mineral surfaces. However, these surfactants lead to the production of emulsified oil that is extremely stable and difficult to separate by conventional methods. This research characterizes the stability of crude oil mixed with a nonionic surfactant, L24–22, in a brine solution. When subjected to gravity separation, a middle oil-rich and bottom water-rich emulsion are generated for various water–oil ratios. Thermal treatments can effectively break oil-rich emulsions, but the bottom water layer remains contaminated with micron-sized crude oil droplets. A magnetic nanoparticle treatment is shown to demulsify the crude oil emulsions, dropping the total organic carbon (TOC) in the water layer from 1470 to 30 ppm.
Prelithiation Effects in Enhancing Silicon-Based Anodes for Full-Cell Lithium-Ion Batteries Using Stabilized Lithium Metal Particles
(American Chemical Society, 2023) Nguyen, Quan Anh; Haridas, Anulekha K.; Terlier, Tanguy; Biswal, Sibani Lisa
Silicon (Si) has been considered as one of the most promising replacements for graphite anodes in next-generation lithium-ion batteries due to its superior specific capacity. However, the irreversible consumption of lithium (Li) ions in Si-based anodes, which is associated with a large volume expansion upon lithiation and the continuous formation of the solid electrolyte interphase (SEI), is especially detrimental to full-cell batteries, whose Li-ion reserve is limited. This study demonstrates the application of stabilized lithium metal particles (SLMPs) as a prelithiation method for Si anodes that can be readily incorporated into large-scale industrial battery manufacturing. Particularly, a surfactant-stabilized SLMP dispersion was designed to be spray-coated onto prefabricated Si composite anodes, forming a uniformly distributed and well-adhered SLMP layer for in situ prelithiation. In full-cells with lithium iron phosphate (LFP) cathodes, the Si-based anodes demonstrated an improved 1st cycle Coulombic efficiency and cycle life with SLMP prelithiation using capacity-control cycling. However, when cycling over the full potential range, prelithiation with high SLMP loading was found to initially increase battery capacity while inducing accelerated fading in later cycles. This phenomenon was caused by Li trapping in the Li–Si alloy associated with higher SLMP-enabled Li diffusion kinetics. Additionally, cycled Si anodes from full-cells were also examined by surface analysis techniques, X-ray photoelectron spectroscopy (XPS) and time-of-flight secondary ion mass spectrometry (ToF-SIMS), demonstrating SLMP effects in modifying the SEI by increasing the inorganic content, particularly LiF, which had been widely credited with improving SEI morphology and Li-ion diffusion through the interphase. Our findings provide valuable insights into the design of prelithiation and cycling strategies for high-capacity Si-based full-cell batteries to utilize the benefits of SLMP while avoiding the Li trapping phenomenon.
Three-dimensional covalent organic frameworks with pto and mhq-z topologies based on Tri- and tetratopic linkers
(Springer Nature, 2023) Zhu, Dongyang; Zhu, Yifan; Chen, Yu; Yan, Qianqian; Wu, Han; Liu, Chun-Yen; Wang, Xu; Alemany, Lawrence B.; Gao, Guanhui; Senftle, Thomas P.; Peng, Yongwu; Wu, Xiaowei; Verduzco, Rafael
Three-dimensional (3D) covalent organic frameworks (COFs) possess higher surface areas, more abundant pore channels, and lower density compared to their two-dimensional counterparts which makes the development of 3D COFs interesting from a fundamental and practical point of view. However, the construction of highly crystalline 3D COF remains challenging. At the same time, the choice of topologies in 3D COFs is limited by the crystallization problem, the lack of availability of suitable building blocks with appropriate reactivity and symmetries, and the difficulties in crystalline structure determination. Herein, we report two highly crystalline 3D COFs with pto and mhq-z topologies designed by rationally selecting rectangular-planar and trigonal-planar building blocks with appropriate conformational strains. The pto 3D COFs show a large pore size of 46 Å with an extremely low calculated density. The mhq-z net topology is solely constructed from totally face-enclosed organic polyhedra displaying a precise uniform micropore size of 1.0 nm. The 3D COFs show a high CO2 adsorption capacity at room temperature and can potentially serve as promising carbon capture adsorbents. This work expands the choice of accessible 3D COF topologies, enriching the structural versatility of COFs.
Revealing the Dual-Layered Solid Electrolyte Interphase on Lithium Metal Anodes via Cryogenic Electron Microscopy
(American Chemical Society, 2023) Wi, Tae-Ung; Park, Sung O; Yeom, Su Jeong; Kim, Min-Ho; Kristanto, Imanuel; Wang, Haotian; Kwak, Sang Kyu; Lee, Hyun-Wook
It is crucial to comprehend the effect of the solid electrolyte interphase (SEI) on battery performance to develop stable Li metal batteries. Nonetheless, the exact nanostructure and working mechanisms of the SEI remain obscure. Here, we have investigated the relationship between electrolyte components and the structural configuration of interfacial layers using an optimized cryogenic transmission electron microscopy (Cryo-TEM) analysis and theoretical calculation. We revealed a unique dual-layered inorganic-rich nanostructure, in contrast to the widely known simple specific component-rich SEI layers. The origin of stable Li cycling is closely related to the Li-ion diffusion mechanism via diverse crystalline grains and numerous grain boundaries in the fine crystalline-rich SEI layer. The results can elucidate a particular issue pertaining to the chemical structure of SEI layers that can induce uniform Li diffusion and rapid Li-ion conduction on Li metal anodes, developing stable Li metal batteries.
High Strength Titanium with Fibrous Grain for Advanced Bone Regeneration
(Wiley, 2023) Wang, Ruohan; Wang, Mingsai; Jin, Rongrong; Wang, Yanfei; Yi, Min; Li, Qinye; Li, Juan; Zhang, Kai; Sun, Chenghua; Nie, Yu; Huang, Chongxiang; Mikos, Antonios G.; Zhang, Xingdong
Pure titanium is widely used in clinical implants, but its bioinert properties (poor strength and mediocre effect on bone healing) limit its use under load-bearing conditions. Modeling on the structure of collagen fibrils and specific nanocrystal plane arrangement of hydroxyapatite in the natural bone, a new type of titanium (Ti) with a highly aligned fibrous-grained (FG) microstructure is constructed. The improved attributes of FG Ti include high strength (≈950 MPa), outstanding affinity to new bone growth, and tight bone-implant contact. The bone-mimicking fibrous grains induce an aligned surface topological structure conducive to forming close contact with osteoblasts and promotes the expression of osteogenic genes. Concurrently, the predominant Ti(0002) crystal plane of FG Ti induces the formation of hydrophilic anatase titanium oxide layers, which accelerate biomineralization. In conclusion, this bioinspired FG Ti not only proves to show mechanical and bone-regenerative improvements but it also provides a new strategy for the future design of metallic biomaterials.

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