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At least 1,027 records · Page 57

Ammonium sulfate leaching of NaOH-treated monazite

Rare earth elements (REEs) can be extracted from monazite under aggressive decomposition and leaching conditions. Much of the waste rocks are removed prior to the extraction process to minimize the costs and waste generation, which is difficult with coal byproducts. The possibility of extracting REEs from low-grade monazite concentrates under relatively mild conditions has been explored to simulate the extraction of REEs from coal byproducts. It has been found that monazite can be decomposed in 10 to 50 % NaOH solutions at 80 °C, with the resulting hydrous oxide being subjected to the ammonium sulfate leaching at pH 4. Further, the ς-potential measurements conducted in the presence of the lixiviant suggest that the NH 4+ ions displace the hydrated Ln 3+ ions from the surface of Ln(OH) 3 (s) by an ion-exchange mechanism, which may be driven by the large differences in the hydration enthalpies between the charged species involved. This approach may be advantageous over acid leaching, including the regeneration of spent lixiviant, lower chemical consumption, and leaching at higher pH.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Electro-strengthening of the additively manufactured Ti–6Al–4V alloy

Structure-property-processing relationship has been studied in additively manufactured Ti–6Al–4V alloy. The processing was performed using in-situ electron microscope (EM) at a moderate current density of 5 × 105 A/cm2 applied for 5 min, and by suppressing Joule heating with massive heat sinks such that the temperature rise was <180 °C and the mechanical properties were not compromised. Overall, the results show that while the grain size increased by ~15%, the nanohardness increased by 16%. This is attributed to the pronounced dislocation generation, regeneration, and clustering as well as defect healing. Ultimately, there is a reduction in the residual strain and a significant increase in the intrinsic strength as evidenced by the high Taylor factor of the electric current processed specimen. This novel processing technique represents an alternative pathway for active controlling of microstructure and internal defects for parts that might be sensitive to high-temperature processing or conventional methods.

36 MATERIALS SCIENCE↗

Hydraulic performance and wave transmission through nature-inspired perforated hollow-base piles breakwater

Nature-based Solutions (NbS) are critical to achieving long-term sustainable coastlines in deltaic coastlines, particularly susceptible to severe impacts under climate change. In recent years, coastal erosion has accelerated in the Vietnam Mekong Delta (VMD), particularly in the West Sea (from Ca Mau to Kien Giang). Due to the characteristics of muddy coastlines and eroded mangrove forests in this region, only a few engineering solutions have effectively reduced waves and promoted sediment accumulation to facilitate beach accretion. However, these solutions require significant investment and cannot be relocated or reused. Therefore, this study introduces a coastal mangrove-inspired perforated hollow-base piles breakwater (PHBPB), which uses the principle of biomimicry by studying the ability of mangrove groups to protect the coastline, stimulate sediment deposition, and over time, restore mangrove forests in the VMD. The hydraulic parameters of PHBPB were tested in 260 scenarios using a physical model, which included varying parameters such as crest width (B), pile row numbers (n c ), crest freeboard (R c ), and wave parameters (H s , T p ) in determining the capabilities of wave transmission, reflection, and wave dissipation. The results showed that the process of wave energy dissipation through perforated hollow-base breakwaters without piles (PHBBWP) is governed by three main parameters, including the relative water depth of the crest (R c /H m0,i ), the relative width of the crest (B/H m0,i ), and the wave slope at the structure location (s m = H m0,i /L m ). In contrast, for PHBPB, the primary influencing factors are the relative submergence depth or the length of the submerged pile portion (R c /H m0,i ) and the relative width of the pile system (X b /L m ). Finally, the hollow structure is suitable for the soft, weak mud geology in this region with poor load-bearing capacity, allows for rapid installation, is reasonably cost-effective, and can be relocated and reused once regeneration has been completed in each stretch of coastline.

54 ENVIRONMENTAL SCIENCES↗

Toward solar light-driven photochemical carbon dioxide separation

The feasibility of energy-efficient photochemically driven CO 2 release has been demonstrated in several recent reports, but the regeneration step remains much slower. Recently in Chem, Ahmad et al. reported a fully visible-light-driven CO 2 separation system capable of operating with concentrated sunlight. Here, we discuss this advance and the potential route toward large-scale fully photochemical CO 2 capture.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Measurement of inclusive $J/ψ$ production in Au+Au collisions at $\sqrt{s_{\textrm{NN}}}$ = 54.4 GeV at STAR

This article presents measurements of inclusive J/ψ production at midrapidity (|y| < 1.0) in Au+Au collisions at $\sqrt{s_{\textrm{NN}}}$ = 54.4 GeV with the STAR detector at the Relativistic Heavy Ion Collider. A suppression of the J/ψ yield, quantified using the nuclear modification factors (R AA , R CP ), is observed with respect to the scaled production p + p in collisions. The dependence of R AA on collision centrality and J/ψ transverse momentum is measured with improved precision compared to previous measurements at 39 and 62.4 GeV, while the centrality dependence of R CP is measured and compared to the same results at 39, 62.4, and 200 GeV. In central collisions, no significant collision energy dependence of R AA is found within uncertainties for collision energies between 17.3 and 200 GeV. Two transport model calculations that include dissociation and regeneration contributions are consistent with the experimental results within uncertainties. Although no significant collision energy dependence of the J/ψ suppression in high energy heavy-ion collisions up to $\sqrt{s_{\textrm{NN}}}$ = 200 GeV is observed within uncertainties, the newly measured results at 54.4 GeV Au+Au collisions provide additional constraints on theoretical calculations of the hot medium evolution and cold nuclear matter effects.

73 NUCLEAR PHYSICS AND RADIATION PHYSICS↗

Styrene Thermal Decomposition and Its Reaction with Acetylene under Shock Tube Pyrolysis Conditions: an Experimental and Kinetic Modeling Study

Styrene is an important compound for polymer production and a key intermediate in gas-phase kinetics of polycyclic aromatic hydrocarbons (PAHs). For the first time, the pyrolysis of styrene with and without the presence of acetylene is investigated in a single-pulse shock tube coupled to gas chromatography and mass spectrometry. For each reaction system, quantitative speciation profiles are probed within the temperature range of 1100-1730 K, nominal pressure of 20 bar, and reaction duration of similar to 4 ms. A kinetic model is built to simulate the results. The model explains how styrene is consumed under high-pressure pyrolytic conditions, how the secondary chemistry of intermediate products affect subsequent PAH formation, and how acetylene addition alters the reaction pathways. Throughout the temperature range, styrene breakdown is dominated by the bimolecular interaction between styrene and hydrogen atom, which produces benzene+vinyl or phenyl and ethylene through the stabilization of 2-phenylethyl and its subsequent dissociation. As a result, large amounts of phenyl accumulate, which react with styrene to form C14H12 species while simultaneously releasing H atoms through addition/elimination reactions. The reactivity of fuel consumption is preserved by the regeneration of H atoms as chain carriers. Several C14H10 compounds are formed as a result of the following breakdown of the C14H12 isomers, particularly stilbene, 1,1-diphenyl ethylene, and 9-methyl-9H-fluorene. The presence of acetylene as a co-reactant with styrene allows the Hydrogen-Abstraction-Acetylene-Addition (HACA) pathway to proceed from phenyl radical to enhance the production of phenylacetylene at very low temperatures and acenaphthylene. This hinders the formation of C14H12 isomers, exclusive products from pure styrene dissociation by competing with the styrene+phenyl routes.

Kinetic Modeling↗

Thermoluminescence and optically stimulated luminescence response of Al 2 O 3 coatings deposited by mist-chemical vapor deposition

Aluminum oxide (Al 2 O 3 ) is a widely used ceramic material which can be applied as a protective coating on metallic structures to improve corrosion resistance and mechanical properties. Al 2 O 3 also has great potential as a functional thin film device in optoelectronics. When it is doped with carbon (Al 2 O 3 :C), this material system can serve as a reliable radiation dosimeter. The combination of optoelectronic, dosimetric, and protective properties demonstrated by Al 2 O 3 uniquely positions it for dual use applications in nuclear forensics, nonproliferation and safeguards, emergency response, retrospective dosimetry, and nondestructive inspection. Here, in this study, an innovative ultrasonic mist-chemical vapor deposition (Mist-CVD) system was used to deposit thin (nm level) Al 2 O 3 coatings on 304 stainless steel substrates. The single aliquot regeneration (SAR) and additive dose reconstruction techniques were then used to investigate the thermoluminescence (TL) and optically stimulated luminescence (OSL) response of the coated substrates to increasing doses of β irradiation. This study demonstrates that nm-thick Al 2 O 3 coatings hold promise as novel nano-dosimeters which could be leveraged for a series of applications such as nonproliferation and safeguards, retrospective dosimetry, and nondestructive inspection.

38 RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEA↗

Electrochemical-assisted leaching of active materials from lithium ion batteries

The development of a circular economy for lithium-ion batteries (LIB) is essential to realize decarbonization and an electrified energy market. However, the current commercial operations that recover valuable constituents from LIBs require significant energy and reagents, which create toxic emissions and additional waste. We report an electrochemical-based method for leaching valuable metals from the active materials of mixed shredded LIBs. In this process, the use electrons, as green reagent, allows the use and regeneration of Fe 2+ in low concentrations as substitute for hydrogen peroxide as a reducing agent. Leaching in a membrane separated two-compartment electrochemical cell contributes to decrease the acid requirements as H+ can be generated electrochemically. With this design, leaching efficiencies over 96% for the active metals (Li, Co, Mn, and Ni) were demonstrated at pulp densities up to 240 g/L. Copper present in the active material is electrowon and recovered separately. Preliminary cost analyses demonstrate ca. 80% reduction in energy and chemical costs as compared to traditional hydrometallurgical routes.

25 ENERGY STORAGE↗

Electrochemical leaching of critical materials from lithium-ion batteries: A comparative life cycle assessment

The manufacturing of lithium-ion batteries (LIB) requires critical materials such as cobalt (Co) and lithium (Li) that are essential for clean-energy products including electric vehicles. Because of their rapidly increasing demand and limited supply, the recycle and reuse of these materials from end-of-life LIB have garnered a lot of interest. Electrochemical leaching has emerged as a sustainable method to extract critical materials out of LIBs, so life cycle assessment was conducted to compare the environmental impacts with traditional peroxide-based leaching and another emerging technology – SO 2 -based leaching. The results showed that electrochemical leaching reduces the global warming potential (GWP) by 80%-87% compared to peroxide-based leaching due to a lower acid consumption, avoidance of hydrogen peroxide, and regeneration of reducing agent iron (II) sulfate and compares well with SO 2 -based leaching in most impact categories. Furthermore, the analysis suggested renewable energy can further reduce the environment footprint of electrochemical leaching.

36 MATERIALS SCIENCE↗

Forest structure and solar-induced fluorescence across intact and degraded forests in the Amazon

Tropical forest degradation (e.g., anthropogenic disturbances such as selective logging and fires) alters forest structure and function and influences the forest's carbon sink. In this study, we explored structure-function relationships across a variety of degradation levels in the southern Brazilian Amazon by 1) investigating how forest structural properties vary as a function of degradation history using airborne lidar data; 2) assessing the effects of degradation on solar-induced chlorophyll fluorescence (SIF) seasonality using TROPOMI data; and 3) quantifying the contribution of structural variables to SIF using multiple regression models with stepwise selection of lidar metrics. Forest degradation history was obtained through Landsat time-series classification. We found that fire, logging, and time since disturbance were major determinants of forest structure, and that forests affected by fires experienced larger variability in leaf area index (LAI), canopy height and vertical structure relative to logged and intact forests. Moreover, only recently burned forests showed significantly depressed SIF during the dry season compared to intact forests. Canopy height and the vertical distribution of foliage were the best predictors of SIF. Unexpectedly, we found that wet-season SIF was higher in active regenerating forests (~ 4 years after fires or logging) compared with intact forests, despite lower LAI. Furthermore, our findings help to elucidate the mechanisms of carbon accumulation in anthropogenically disturbed tropical forests and indicate that they can capture large amounts of carbon while recovering.

54 ENVIRONMENTAL SCIENCES↗

Desiccants enabling energy-efficient buildings: A review

Buildings account for about 39% of the total energy consumption in the United States. Developing highly energy-efficient and environmentally friendly systems that are either actively or passively integrated into buildings plays a crucial role in decarbonizing the building sector. Among various technologies, desiccant-based energy systems have received particular attention in recent years due to their unique advantages, such as being thermally driven using low-grade waste or solar energies and being reliable over a wide range of operating ranges. Extensive research efforts have been exerted on desiccant-enabled technologies at both material and system levels aiming to increase their performance and achieve high technological readiness levels. The present review paper comprehensively discusses research works made at the system level. It overviews desiccant-based air conditioning systems, desiccant-based humidity pumps, desiccant-based thermal energy storage systems, and desiccant-based appliances. The study identifies challenges and opportunities to accelerate the commercialization of desiccant-enabled technologies. It is found that desiccant materials offer great promise to improve energy efficiency and functionality of future buildings through decoupling the latent and sensible cooling loads in air conditioning systems, humidity pumps integrated into building facades, and next-generation appliances. However, commercial viability and widespread acceptance of desiccant-based systems have been hampered by several major obstacles, including liquid and air flow mal-distribution and inferior thermo-physical properties of desiccant materials resulting in low ab/adsorption and regeneration rates and bulky/costly systems.

25 ENERGY STORAGE↗

Measurement of free chlorine levels in water using potentiometric responses of biofilms and applications for monitoring and managing the quality of potable water

We report residual free chlorine is not monitored continuously at scale in drinking water distribution systems because existing real-time sensor technologies require frequent maintenance, cleaning, and calibration, which makes these products too costly to be used throughout a distribution system. As a result, current measurement approaches require manual sampling, which is not feasible for the consistent monitoring of free chlorine because chlorine concentrations vary significantly throughout pipeline distribution and over time and space. This research presents an alternative and cost-effective method of predicting free chlorine levels in drinking water using graphite electrodes coated with naturally grown microbial biofilms. This Microbial Potentiometric Sensor (MPS) array was installed in a Continuously Mixed Batch Reactor (CMBR), and drinking water containing variable free chlorine concentrations. The chlorine concentrations were introduced in a controlled manner, and the MPS signals were monitored over time. MPS signals were measured from the change in Open Circuit Potential (OCP) across the MPS array in real-time. An empirically derived relationship between the normalized change in OCP and free chlorine was established by fitting individual and average MPS data to a decaying exponential growth function in order to predict free chlorine levels. The results show that free chlorine can be predicted with reasonable accuracy, with model validation showing an average absolute error of ±0.09 ppm below 1.1 ppm and ±0.30 ppm between 1.1 and 2.7 ppm. However, the accuracy of predictions was reduced at higher free chlorine levels. The researchers conclude that MPS systems may benefit drinking water distribution systems by measuring free chlorine. These advantages of the MPS are especially pronounced in the developing world because this system is inexpensive and does not require routine maintenance or cleaning. The system relies on a naturally forming and regenerating biofilm and an inexpensive potentiometric meter to produce stable measurements.

54 ENVIRONMENTAL SCIENCES↗

Electrochemical leaching of spent LIBs: Kinetics, novel reactor, and modeling

The use of electrons as main reagent for the recovery and recycling of critical metals from spent lithium-ion batteries (LIBs) is a process electrification strategy that can be used to close the life-cycle loop of LIBs through more sustainable methods. Electrochemical leaching, a process that uses a reductant that is constantly regenerated electrochemically for the leaching of lithium-ion battery black mass (LIBBM), has shown high extraction efficiencies and sustainable scores. However, slow kinetics, reactor design challenges and lack of deeper understanding of the underlying processes are barriers to the optimization, scale-up, and market adoption of this technology. In this paper, a kinetic study and mathematical model for dissolving LIBBM is presented to better understand the underlying mechanisms aiming to reduce the processing time and make predictions for future design and scale-up. The effect of acid and electrochemically mediated reductant concentrations, LIBBM loading, and cathode/reactor designs were explored. As a result, the leaching time was reduced from 7h to under 1h at a pulp density of 73 g/L, without external heating. A novel reactor with parallel baffle electrodes (PBE) was developed, which significantly reduced the leaching time by improving convection in a stirred slurry electrochemical reactor. Dimensionless numbers were deduced from an unsteady state model, which can be used in dimensional analysis for future process design and scale-up.

25 ENERGY STORAGE↗

Designing clay-polymer nanocomposite sorbents for water treatment: A review and meta-analysis of the past decade

Clay-polymer nanocomposites (CPNs) have been studied for two decades as sorbents for water pollutants, but their applicability remains limited. Our aim in this review is to present the latest progress in CPN research using a meta-analysis approach and identify key steps necessary to bridge the gap between basic research and CPN application. Based on results extracted from 99 research articles on CPNs and 8 review articles on other widely studies sorbents, CPNs had higher adsorption capacities for several inorganic and organic pollutant classes (including heavy metals, oxyanions, and dyes, n = 308 observations). We applied principal component analysis, analysis of variance, and multiple linear regressions to test how CPN and pollutant properties correlated with Langmuir adsorption model coefficients. While adsorption was, surprisingly, not influenced by mineral properties, it was influenced by CPN fabrication method, polymer functional groups, and pollutant properties. For example, among the pollutant classes, heavy metals had the highest adsorption capacity but the lowest adsorption affinity. Conversely, dyes had high adsorption affinities, as reflected by the linear correlation between adsorption affinity and pollutant molecular weight. Scaling from ‘basic research’ to ‘technological application’ requires testing CPN performance in real water, application in columns, comparison to commercial sorbents, regeneration, and cost evaluation. However, our survey indicates that of the 158 observations, only 20 compared the CPN's performance to that of a commercial sorbent. We anticipate that this review will promote the design of smart and functional CPNs, which can then evolve into an effective water treatment technology.

42 ENGINEERING↗

Controlling selectivity of modular microbial biosynthesis of butyryl-CoA-derived designer esters

Short-chain esters have broad utility as flavors, fragrances, solvents, and biofuels. Controlling selectivity of ester microbial biosynthesis has been an outstanding metabolic engineering problem. In this study, we enabled the de novo fermentative microbial biosynthesis of butyryl-CoA-derived designer esters (e.g., butyl acetate, ethyl butyrate, butyl butyrate) in Escherichia coli with controllable selectivity. Using the modular design principles, we generated the butyryl-CoA-derived ester pathways as exchangeable production modules compatible with an engineered chassis cell for anaerobic production of designer esters. We designed these modules derived from an acyl-CoA submodule (e.g., acetyl-CoA, butyryl-CoA), an alcohol submodule (e.g., ethanol, butanol), a cofactor regeneration submodule (e.g., NADH), and an alcohol acetyltransferase (AAT) submodule (e.g., ATF1, SAAT) for rapid module construction and optimization by manipulating replication (e.g., plasmid copy number), transcription (e.g., promoters), translation (e.g., codon optimization), pathway enzymes, and pathway induction conditions. To further enhance production of designer esters with high selectivity, we systematically screened various strategies of protein solubilization using protein fusion tags and chaperones to improve the soluble expression of multiple pathway enzymes. Finally, our engineered ester-producing strains could achieve 19-fold increase in butyl acetate production (0.64 g/L, 96% selectivity), 6-fold increase in ethyl butyrate production (0.41 g/L, 86% selectivity), and 13-fold increase in butyl butyrate production (0.45 g/L, 54% selectivity) as compared to the initial strains. Altogether, this study presented a generalizable framework to engineer modular microbial platforms for anaerobic production of butyryl-CoA-derived designer esters from renewable feedstocks.

59 BASIC BIOLOGICAL SCIENCES↗

Hybrid biological-chemical strategy for converting polyethylene into a recyclable plastic monomer using engineered Corynebacterium glutamicum

Converting polyethylene (PE) into valuable materials, particularly ones that are better for the environment than the incumbent plastics, not only helps mitigate environmental issues caused by plastic waste but also alleviates the long-standing problem of microbial fermentation competing with food supplies. However, the inherent robustness of PE due to its strong carbon-carbon bonds and high molecular weight necessitates harsh decomposition conditions, resulting in diverse decomposition outcomes that present significant challenges for downstream applications, especially for bioconversion. In this study, we demonstrate a hybrid biological-chemical conversion process for PE, converting its decomposition products, namely short-chain diacids, into a monomer, β-keto-δ-lactone (BKDL), for highly recyclable polydiketoenimine plastics using engineered Corynebacterium glutamicum. Since BKDL synthesis requires a substantial supply of malonyl-CoA, we employed an alternative biosynthesis pathway that leverages C. glutamicum's natural proficiency in amino acid production. We optimized this pathway in vivo by minimizing carbon loss to CO2 and byproducts, improving the transporter system, and maximizing co-factor regeneration. Furthermore, we co-optimized the PE deconstruction process to produce predominantly C4 to C6 diacids and integrated three catabolic pathways into the engineered strain to enhance diacid utilization, maximizing the carbon conversion from PE. Finally, an engineered polyketide synthase was introduced into C. glutamicum to enable BKDL synthesis. This work demonstrates the potential of a chemo-biological hybrid strategy for recycling plastic waste, highlighting its promise in addressing environmental challenges and promoting sustainable materials.

Zhan, Chunjun↗

PET-FBA: A lightweight enzyme allocation and thermodynamics-constrained flux analysis approach to explore Escherichia coli metabolic adaptation to intracellular acidification

Escherichia coli employs diverse strategies to adapt to acidic environments that disrupt enzyme activity and the thermodynamic feasibility of essential reactions. To understand the impact of pH stress on cell metabolism, we present the PET-FBA (pH-, Enzyme protein allocation-, and Thermodynamics-constrained Flux Balance Analysis) framework. PET-FBA extends genome-scale modeling by integrating enzyme protein costs and reaction Gibbs free energy changes. Additionally, by incorporating pH-dependent enzyme kinetics in response to intracellular acidification, this framework enables the simulation of E. coli's metabolic adjustments across varying external pH levels. The model's accuracy is validated by comparing in silico growth simulations with experimental measurements under both anaerobic and aerobic conditions, as well as in silico gene knockouts of essential genes. By explicitly incorporating pH effects, our model accurately replicates the metabolic shift towards lactate production as the primary fermentation product at low pH in anaerobic conditions. This shift is only predicted when enzyme kinetics are dynamically adjusted as a function of pH. Further analysis revealed that this shift can be attributed to the reduced protein efficiency of the acetyl-CoA branch compared to lactate dehydrogenase under acidic stress, which then becomes crucial for maintaining NAD regeneration and cell growth at low pH. Furthermore, we identified strategies for enhancing cell growth under acidic anaerobic conditions by improving the enzyme activity of lactate dehydrogenase and pyruvate formate lyase, which increases NAD production efficiency and reduces enzyme protein allocation costs. Designed as a lightweight yet versatile framework, PET-FBA enables efficient genome-scale metabolic analysis. Using E. coli as a model system, our framework provides a systematic approach to understanding metabolic responses to environmental stress, pinpointing key metabolic bottlenecks, and identifying potential targets for strain optimization.

42 ENGINEERING↗

Hydrogen-Bonded Organic Frameworks: A Rising Class of Porous Molecular Materials

Hydrogen-bonded organic frameworks (HOFs) are a class of porous molecular materials that rely on the assembly of organic building blocks by means of hydrogen-bonding interactions to form two-dimensional (2D) and three-dimensional (3D) crystalline networks. The reversible nature of the hydrogen-bond formation endows HOFs with the attributes of solution processability and simple regeneration. High-quality single crystals of HOFs can be grown easily for unambiguous superstructure determination by single-crystal X-ray diffraction, which is crucial for the elucidation of superstructure–property relationships. During the past decade, considerable progress has been achieved in realizing stable HOFs with permanent porosities by focusing on the design of molecular building blocks in order to introduce rigidity, auxiliary [π···π] interactions, and interpenetration of their frameworks to sustain the extended networks. The applications of HOFs are far-reaching, spanning catalysis, energy, and biomedical products as well as the storage and separation of fine chemicals. In this paper, we, first of all, provide an overview of the chronological development of HOFs, starting from the seminal work by Marsh and Duchamp in 1969 on the crystal superstructure of the hydrogen-bonded networks of trimesic acid. We identify the development of novel hydrogen-bonding motifs such as diaminotriazine (DTA), the introduction of the concept of molecular tectonics, and the establishment of permanent porosity in HOFs as being some of the milestones, which incentivized the current burgeoning research endeavors on developing HOFs as multifunctional materials. This Account is focused primarily on surveying the strategies for constructing porous 3D HOFs based on organic building blocks with peripheral carboxyl groups. These strategies are presented in the following categories: (1) the polycatenation of 2D networks by trigonal building blocks to form global 3D frameworks, (2) the utilization of building blocks with 3D geometries—tetrahedral and trigonal prismatic—that are predisposed to form 3D networks, and (3) the docking by shape-fitting of geometrically labile building blocks. We emphasize how the molecular geometry of the building blocks plays an important role in modulating the superstructures of extended frameworks so as to address specific applications. Recognizing that the in silico design of HOFs is the ultimate goal of researchers in this field, we also discuss the recent advances in superstructure prediction that lead to the formation of porous supramolecular crystals and assess the complications in implementing computational methods for HOFs with complex superstructures. We hope this Account will inspire the development of new supramolecular designs and creative approaches to crystal engineering that aid and abet the assembly of multifunctional HOFs with customizable properties.

36 MATERIALS SCIENCE↗