Systems Engineering Research Center

This critical review investigates the potential for membrane distillation to desalinate high-salinity waters using low-grade heat at the water-energy nexus.

Advanced oxidation processes via semiconductor photocatalysis for water treatment have been the subject of extensive research over the past three decades, producing many scientific reports focused on elucidating mechanisms and enhancing kinetics for the treatment of contaminants in water. Many of these reports imply that the ultimate goal of the research is to apply photocatalysis in municipal water treatment operations. However, this ignores immense technology transfer problems, perpetuating a widening gap between academic advocation and industrial application. In this Feature, we undertake a critical examination of the trajectory of photocatalytic water treatment research, assessing the viability of proposed applications and identifying those with the most promising future. Several strategies are proposed for scientists and engineers who aim to support research efforts to bring industrially relevant photocatalytic water treatment processes to fruition. Although the reassessed potential may not live up to initial academic hype, an unfavorable assessment in some areas does not preclude the transfer of photocatalysis for water treatment to other niche applications as the technology retains substantive and unique benefits.

In recent years, the concepts of resilience and sustainability have become very topical and popular. The concept of sustainability rose to prominence in the late 1980s and became a central issue in world politics, when the construction industry began to generate the first sustainable building assessment systems with more or less equally weighted environmental, economic, and social aspects for office buildings over their life cycles. On the other hand, resilience is usually connected to the occurrence of extreme events during the life cycle of structures and infrastructures. In the last decade, it has been used to minimize specifically direct and indirect losses from hazards through enhanced resistance and robustness to extreme events, as well as more effective recovery strategies. A detailed comparison of the studies dealing with either infrastructure sustainability or resilience presented in this paper leads to the conclusion that they have a vast number of similarities and common characteristics. For instance, they both combine structural analyses with social and economic aspects; they both rely on techniques for the life-cycle analysis and decision making; they both are in an early stage, where the academic world is trying to find the best way to promote the application of the scientific results among professional engineers and the industry. Indeed, both approaches try to optimize a system, such as a civil infrastructure system, with respect to structural design, utilized material, maintenance plans, management strategies, and impacts on the society. However, for the most part, researchers and practitioners focusing on either resilience or sustainability operate without a mutual consideration of the findings, which leads to a severe inefficiency. Therefore, this paper suggests that resilience and sustainability are complementary and should be used in an integrated perspective. In particular, the proposed approach is rooted in the well-established framework of risk assessment. The impact of the infrastructure and its service states on the society in normal operational conditions (assessed by sustainability analysis) and after exceptional events (assessed by resilience analysis) should be weighted by the associated probabilities of occurrence and combined in a global impact assessment. The proposed perspective and assessment technique is applicable to various types of civil infrastructure systems, but the case of transportation networks and bridge systems is emphasized herein. A numerical application dealing with the comparative analysis of two possible bridge layouts is presented to exemplify the approach. The results show that both resilience and sustainability analyses assess a relevant amount of the impact of the bridge on the community where it is built, so neither one can be neglected.

and Pt catalysts and kept at least 90% of the initial current applied after 20 000 s for the OER/ORR/HER reactions. This study reveals significant insight about the structure-function relationship for non-noble bimetallic nanostructures with multifunctional electrocatalytic properties.

Using a bipolymer system consisting of polyvinylpyrrolidone (PVP) and poly(vinylidene fluoride) (PVDF), P25-TiO2 was immobilized into thin film mats of porous electrospun fibers. Pores were introduced by dissolving sacrificial PVP to increase surface area and enhance access to TiO2. The highest photocatalytic activity was achieved using a PVDF:PVP weight ratio of 2:1. Methylene blue (MB) was used to visualize contaminant removal, assess the sorption capacity (5.93 ± 0.23 mg/g) and demonstrate stable removal kinetics (kMB > 0.045 min–1) under UVA irradiation (3.64 × 10–9 einstein/cm2/s) over 10 cycles. Treatment was also accomplished via sequential MB sorption in the dark and subsequent photocatalytic degradation under UVA irradiation, to illustrate that these processes could be uncoupled to overcome limited light penetration. The photocatalytic mat degraded bisphenol A and 17α-ethynylestradiol in secondary wastewater effluent (17 mg TOC/L), and (relative to TiO2 slurry) immobilization of TiO2 in the mat mitigated performance inhibition by co-occurring organics that scavenge oxidation capacity. This significantly lowered the electrical energy-per-order of reaction (EEO) needed to remove such endocrine disruptors in the presence of oxidant scavenging/inhibitory organics. Thus, effective TiO2 immobilization into polymers with affinity toward specific priority pollutants could both increase the efficiency and reduce energy requirements of photocatalytic water treatment.

We reveal the insignificance of advanced materials in further enhancing the energy efficiency of desalination and suggest more impactful approaches.

This review provides the fundamental and essential knowledge of UV-LEDs to better apply LED technology in environmental application.

In this study, we present a facile and scalable approach to fabricate omniphobic nanofiber membranes by constructing multilevel re-entrant structures with low surface energy. We first prepared positively charged nanofiber mats by electrospinning a blend polymer-surfactant solution of poly(vinylidene fluoride-co-hexafluoropropylene) (PVDF-HFP) and cationic surfactant (benzyltriethylammonium). Negatively charged silica nanoparticles (SiNPs) were grafted on the positively charged electrospun nanofibers via dip-coating to achieve multilevel re-entrant structures. Grafted SiNPs were then coated with fluoroalkylsilane to lower the surface energy of the membrane. The fabricated membrane showed excellent omniphobicity, as demonstrated by its wetting resistance to various low surface tension liquids, including ethanol with a surface tension of 22.1 mN/m. As a promising application, the prepared omniphobic membrane was tested in direct contact membrane distillation to extract water from highly saline feed solutions containing low surface tension substances, mimicking emerging industrial wastewaters (e.g., from shale gas production). While a control hydrophobic PVDF-HFP nanofiber membrane failed in the desalination/separation process due to low wetting resistance, our fabricated omniphobic membrane exhibited a stable desalination performance for 8 h of operation, successfully demonstrating clean water production from the low surface tension feedwater.

Development of novel adsorbents often neglects the competitive adsorption between co-occurring oxo-anions, overestimating realistic pollutant removal potentials, and overlooking the need to improve selectivity of materials. This critical review focuses on adsorptive competition between commonly co-occurring oxo-anions in water and mechanistic approaches for the design and development of selective adsorbents. Six "target" oxo-anion pollutants (arsenate, arsenite, selenate, selenite, chromate, and perchlorate) were selected for study. Five "competing" co-occurring oxo-anions (phosphate, sulfate, bicarbonate, silicate, and nitrate) were selected due to their potential to compete with target oxo-anions for sorption sites resulting in decreased removal of the target oxo-anions. First, a comprehensive review of competition between target and competitor oxo-anions to sorb on commonly used, nonselective, metal (hydr)oxide materials is presented, and the strength of competition between each target and competitive oxo-anion pair is classified. This is followed by a critical discussion of the different equations and models used to quantify selectivity. Next, four mechanisms that have been successfully utilized in the development of selective adsorbents are reviewed: variation in surface complexation, Lewis acid/base hardness, steric hindrance, and electrostatic interactions. For each mechanism, the oxo-anions, both target and competitors, are ranked in terms of adsorptive attraction and technologies that exploit this mechanism are reviewed. Third, given the significant effort to evaluate these systems empirically, the potential to use computational quantum techniques, such as density functional theory (DFT), for modeling and prediction is explored. Finally, areas within the field of selective adsorption requiring further research are detailed with guidance on priorities for screening and defining selective adsorbents.

The development of low-dimensional (LD) supramolecular materials with multifunctional electrocatalytic properties has sparked the attention of the catalysis community. Herein, we report the synthesis of a new class of 0D–2D heterostructures composed of boron carbon nitride nanosheets (BCN NSs) and fullerene molecules (C60/F) that exhibit multifunctional electrocatalytic properties for the hydrogen evolution/oxidation reactions (HER/HOR) and the oxygen evolution/reduction reactions (OER/ORR). The electrocatalytic properties were studied with varying F:BCN weight ratios to optimize the intermolecular electron transfer (ET) from the BCN NSs to the electron-accepting C60 molecules. The nanohybrid supramolecular material with 10 wt % F in BCN NSs (10% F/BCN) exhibited the largest Raman and C 1s binding energy shifts, which were associated with greater cooperativity interactions and enhanced ET processes at the F/BCN interface. This synergistic interfacial phenomenon resulted in highly active catalytic sites that markedly boosted electrocatalytic activity of the material. The 10% F/BCN showed the highest tetrafunctional catalytic performance, outperforming the OER catalytic activity of commercial RuO2 catalysts with a η10 of 390 mV and very competitive onset potential values of −0.042 and 0.92 V vs RHE for HER and ORR, respectively, and a current density value of 1.47 mA cm–2 at 0.1 V vs RHE with an ultralow ΔGH* value of −0.03 eV toward the HOR process. Additionally, the 10% F/BCN catalyst was also used as both cathode and anode in a water splitting device, delivering a cell potential of 1.61 V to reach a current density of 10 mA cm–2.

Synthetic polymer membranes are enabling components in key technologies at the water-energy nexus, including desalination and energy conversion, because of their high water/salt selectivity or ionic conductivity. However, many applications at the water-energy nexus require ion selectivity, or separation of specific ionic species from other similar species. Here, the ion selectivity of conventional polymeric membrane materials is assessed and recent progress in enhancing selective transport via tailored free volume elements and ion-membrane interactions is described. In view of the limitations of polymeric membranes, three material classes-porous crystalline materials, 2D materials, and discrete biomimetic channels-are highlighted as possible candidates for ion-selective membranes owing to their molecular-level control over physical and chemical properties. Lastly, research directions and critical challenges for developing bioinspired membranes with molecular recognition are provided.

Perfluorooctanesulfonate (PFOS) is a persistent organic pollutant that is bioaccumulative and toxic. While its use in most countries has been restricted to certain industrial applications due to environmental and health concerns, chrome plating and semiconductor manufacturing facilities are industrial point sources of PFOS-containing wastewater. Current remediation technologies are ineffective at treating these highly concentrated industrial effluents. In this work, UiO-66 metal–organic frameworks (MOFs) of several defect concentrations were studied as sorbents for the removal of PFOS from concentrated aqueous solutions. PFOS sorption isotherms indicated that defective UiO-66, prepared with HCl as a modulator, had a maximum Langmuir sorption capacity of 1.24 mmol/g, which was ∼2× greater than powdered activated carbon (PAC), but ∼2× less than that of a commercial ion-exchange resin. Defective UiO-66 adsorbed PFOS 2 orders of magnitude faster than the ion-exchange resin. Large pore defects (∼16 and ∼20 Å) within the framework were critical to the increased adsorption capacity due to higher internal surface area and an increased number of coordinatively unsaturated Zr sites to bind the PFOS head groups. Of the common co-contaminants in chrome plating wastewaters, chloride ions have a negligible effect on PFOS sorption, while sulfate and hexavalent chromium anions compete for cationically charged adsorption sites. These materials were also effective adsorbents for the shorter-chain homologue, perfluorobutanesulfonate (PFBS). The enhanced PFOS and PFBS adsorptive properties of UiO-66 highlight the advantage of structurally defective MOFs as a water treatment approach toward environmental sustainability.

Concern over water contamination by per/polyfluoroalkyl substances (PFAS) has highlighted the lack of effective treatment approaches. Photocatalysis offers advantages of using ambient conditions for reaction, air as the oxidant, and light as the energy source, but identifying photoactive materials is challenging. Herein, we report that boron nitride (BN) degrades PFOA upon irradiation with 254 nm light. The ability of BN to degrade PFOA photocatalytically has previously been unreported and is unexpected, because its band gap is too large for light absorption. On the basis of scavenger results, we suggest that PFOA degrades in the presence of BN via a hole-initiated reaction pathway similar to the TiO2 case and involves superoxide/hydroperoxyl and hydroxyl radicals. We surmised that defects allow BN to absorb in the UVC range and to photogenerate reactive oxygen species. Sealed batch studies indicated BN was ∼2 and ∼4 times more active than TiO2, before and after ball milling the material, respectively. BN can be reused, showing no decrease in activity over three cycles. BN was active for the photocatalytic degradation of GenX, another PFAS of concern. These findings present fresh opportunities for materials design and for the re-evaluation of other wide band gap semiconductors for PFAS photocatalytic degradation.

Single atom catalysts have been found to exhibit superior selectivity over nanoparticulate catalysts for catalytic reactions such as hydrogenation due to their single-site nature. However, improved selectively is often accompanied by loss of activity and slow kinetics. Here we demonstrate that neighboring Pd single atom catalysts retain the high selectivity merit of sparsely isolated single atom catalysts, while the cooperative interactions between neighboring atoms greatly enhance the activity for hydrogenation of carbon-halogen bonds. Experimental results and computational calculations suggest that neighboring Pd atoms work in synergy to lower the energy of key meta-stable reactions steps, i.e., initial water desorption and final hydrogenated product desorption. The placement of neighboring Pd atoms also contribute to nearly exclusive hydrogenation of carbon-chlorine bond without altering any other bonds in organohalogens. The promising hydrogenation performance achieved by neighboring single atoms sheds light on a new approach for manipulating the activity and selectivity of single atom catalysts that are increasingly studied in multiple applications.

A simple heat treatment, perhaps the most globally recognized point-of-use water sterilization method, is seemingly effective against all major pathogens of concern, but bulk water boiling is not energy efficient or sustainable. Herein, we present the first application of solar-to-thermal converting nanomaterials for the direct inactivation of bacteria and viruses in drinking water through the application of Au nanorods, carbon black, and Au nanorod-carbon black composite materials as light absorbers. With broad absorption bands spanning the visible and near-infrared wavelengths, at sufficient concentrations, these nanoparticles induce multiple scattering events, increasing photon absorption probability and concentrating the light within a small spatial domain, leading to localized, intense heating that inactivates microorganisms in close proximity. Moving toward practical device design, we have developed a facile silane immobilization approach to fabricate films with densely packed layers of photothermal nanomaterials. Our results suggest that upon irraditaion with simulated solar light, these films can thermally inactivate bacteria and viruses, as demonstrated through the inactivation of surrogate organisms Escherichia coli K-12, and bacteriophages MS2 and PR772.

Reactive membranes based on hydroxyl radical generation are hindered by the need for chemical dosing and complicated module and material design. Herein, we utilize an electrochemical approach featuring in situ generation of reactive (radical) chlorine species (RCS) through anodization of chloride ions for membrane self-cleaning. A hybridized carbon nanotube (CNT)-functionalized ceramic membrane (h-CNT/CM), possessing high hydrophilicity, permeability, and conductivity, was fabricated. Using carbamazepine (CBZ) as a probe, we confirmed the presence of RCS in the electrified h-CNT/CM. The rapid and complete degradation of CBZ in a single-pass ultrafiltration indicates a high localized RCS concentration within the three-dimensional porous CNT interwoven layer. We further demonstrate that the electrogeneration of RCS is a critical prestep for free chlorine (HClO and ClO–) formation. The self-cleaning efficiency of the membrane after fouling with a model organic foulant (alginate) was assessed using an electrified cross-flow membrane filtration system. The fouled h-CNT/CM exhibits a near complete water flux recovery following a short (1 min) self-cleaning with an applied voltage of 3 or 4 V and feed solutions of 100 or 10 mM sodium chloride, respectively. Considering the superior performance of the RCS-mediated self-cleaning compared to conventional membrane chemical cleaning using sodium hypochlorite, our results exemplify an effective strategy for in situ electrogeneration of RCS to achieve a highly efficient membrane self-cleaning.

There is a growing need to mitigate the discharge of extracellular antibiotic resistance genes (ARGs) from municipal wastewater treatment systems. Here, molecularly-imprinted graphitic carbon nitride (MIP-C3N4) nanosheets were synthesized for selective photocatalytic degradation of a plasmid-encoded ARG (blaNDM-1, coding for multidrug resistance New Delhi metallo-β-lactamase-1) in secondary effluent. Molecular imprinting with guanine enhanced ARG adsorption, which improved the utilization of photogenerated oxidizing species to degrade blaNDM-1 rather than being scavenged by background nontarget constituents. Consequently, photocatalytic removal of blaNDM-1 in secondary effluent with MIP-C3N4 (k = 0.111 ± 0.028 min–1) was 37 times faster than with bare graphitic carbon nitride (k = 0.003 ± 0.001 min–1) under UVA irradiation (365 nm, 3.64 × 10–6 Einstein/L·s). MIP-C3N4 can efficiently catalyze the fragmentation of blaNDM-1, which decreased the potential for ARG repair by transformed bacteria. Molecular imprinting also changed the primary degradation pathway; electron holes (h+) were the predominant oxidizing species responsible for blaNDM-1 removal with MIP-C3N4 versus free radicals (i.e., ·OH and O2–) for coated but nonimprinted C3N4. Overall, MIP-C3N4 efficiently removed blaNDM-1 from secondary effluent, demonstrating the potential for molecular imprinting to enhance the selectivity and efficacy of photocatalytic processes to mitigate dissemination of antibiotic resistance from sewage treatment systems.

Providing access to safe drinking water is a prerequisite for protecting public health. Vast improvements in drinking water quality have been witnessed during the last century, particularly in urban areas, thanks to the successful implementation of large, centralized water treatment plants and the distribution of treated water via underground networks of pipes. Nevertheless, infection by waterborne pathogens through the consumption of biologically unsafe drinking water remains one of the most significant causes of morbidity and mortality in developing rural areas. In these areas, the construction of centralized water treatment and distribution systems is impractical due to high capital costs and lack of existing infrastructure. Improving drinking water quality in developing rural areas demands a paradigm shift to unconventional, innovative water disinfection strategies that are low cost and simple to implement and maintain, while also requiring minimal infrastructure. The implementation of point-of-use (POU) disinfection techniques at the household- or community-scale is the most promising intervention strategy for producing immediate health benefits in the most vulnerable rural populations. Among POU techniques, solar-driven processes are considered particularly instrumental to this strategy, as developing rural areas that lack safe drinking water typically receive higher than average surface sunlight irradiation. Materials that can efficiently harvest sunlight to produce disinfecting agents are pivotal for surpassing the disinfection performance of conventional POU techniques. In this account, we highlight recent advances in materials and processes that can harness sunlight to disinfect water. We describe the physicochemical properties and molecular disinfection mechanisms for four categories of disinfectants that can be generated by harvesting sunlight: heat, germicidal UV radiation, strong oxidants, and mild oxidants. Our recent work in developing materials-based solar disinfection technologies is discussed in detail, with particular focus on the materials' mechanistic functions and their modes of action for inactivation of three common types of waterborne pathogens (i.e., bacteria, virus, and protozoa). We conclude that different solar disinfection technologies should be applied depending on the source water quality and target pathogen due to significant variations on susceptibility of microbial components to disparate disinfectants. In addition, we expect that ample research opportunities exist on reactor design and process engineering for scale-up and improved performance of these solar materials, while accounting for the infrastructure demand and capital input. Although the practical implementation of new treatment techniques will face social and economic challenges that cannot be overlooked, novel technologies such as these can play a pivotal role in reducing water borne disease burden in rural communities in the developing world.

An international workshop identified how pore structures and unique properties that emerge at nano- to sub-nano- size domains can improve the energy efficiency and selectivity of electroseparation or electrocatalytic processes for treating water.

Engineered nanomaterials alone or in combination with other technologies may improve<italic>in situ</italic>subsurface remediation of legacy and emerging contaminants.