Danmeng Shuai

Enhanced activity and selectivity of carbon nanofiber supported Pd catalysts for nitrite reduction

Pd-based catalyst treatment represents an emerging technology that shows promise to remove nitrate and nitrite from drinking water. In this work we use vapor-grown carbon nanofiber (CNF) supports in order to explore the effects of Pd nanoparticle size and interior versus exterior loading on nitrite reduction activity and selectivity (i.e., dinitrogen over ammonia production). Results show that nitrite reduction activity increases by 3.1-fold and selectivity decreases by 8.0-fold, with decreasing Pd nanoparticle size from 1.4 to 9.6 nm. Both activity and selectivity are not significantly influenced by Pd interior versus exterior CNF loading. Consequently, turnover frequencies (TOFs) among all CNF catalysts are similar, suggesting nitrite reduction is not sensitive to Pd location on CNFs nor Pd structure. CNF-based catalysts compare favorably to conventional Pd catalysts (i.e., Pd on activated carbon or alumina) with respect to nitrite reduction activity and selectivity, and they maintain activity over multiple reduction cycles. Hence, our results suggest new insights that an optimum Pd nanoparticle size on CNFs balances faster kinetics with lower ammonia production, that catalysts can be tailored at the nanoscale to improve catalytic performance for nitrite, and that CNFs hold promise as highly effective catalyst supports in drinking water treatment.

Tailored Synthesis of Photoactive TiO2 Nanofibers and Au/TiO2 Nanofiber Composites: Structure and Reactivity Optimization for Water Treatment Applications

Titanium dioxide (TiO2) nanofibers with tailored structure and composition were synthesized by electrospinning to optimize photocatalytic treatment efficiency. Nanofibers of controlled diameter (30-210 nm), crystal structure (anatase, rutile, mixed phases), and grain size (20-50 nm) were developed along with composite nanofibers with either surface-deposited or bulk-integrated Au nanoparticle cocatalysts. Their reactivity was then examined in batch suspensions toward model (phenol) and emerging (pharmaceuticals, personal care products) pollutants across various water qualities. Optimized TiO2 nanofibers meet or exceed the performance of traditional nanoparticulate photocatalysts (e.g., Aeroxide P25) with the greatest reactivity enhancements arising from (i) decreasing diameter (i.e., increasing surface area), (ii) mixed phase composition [74/26 (±0.5) % anatase/rutile], and (iii) small amounts (1.5 wt %) of surface-deposited, more so than bulk-integrated, Au nanoparticles. Surface Au deposition consistently enhanced photoactivity by 5- to 10-fold across our micropollutant suite independent of their solution concentration, behavior that we attribute to higher photocatalytic efficiency from improved charge separation. However, the practical value of Au/TiO2 nanofibers was limited by their greater degree of inhibition by solution-phase radical scavengers and higher rate of reactivity loss from surface fouling in nonidealized matrixes (e.g., partially treated surface water). Ultimately, unmodified TiO2 nanofibers appear most promising for use as reactive filtration materials because their performance was less influenced by water quality, although future efforts must increase the strength of TiO2 nanofiber mats to realize such applications.

Elucidation of Nitrate Reduction Mechanisms on a Pd‐In Bimetallic Catalyst using Isotope Labeled Nitrogen Species

To understand nitrate reduction pathway and to improve selectivity towards dinitrogen (N2) over toxic ammonia species (NH4+, NH3), aqueous reduction experiments with an Al2O3‐supported Pd‐In bimetallic catalyst were conducted by using isotope‐labeled nitrite (15NO2−). Nitrite is the first reduction intermediate of nitrate. Experiments were performed using nitrite alone and in combination with unlabeled proposed reduction intermediates (N2O, NO), and using only N2O and NO alone, each as a starting reactant. Use of 15N‐labeled species eliminates interference from ambient N2 when assessing mass balances and product distributions. Simultaneous catalytic reduction of 15NO2− and 14N2O shows no isotope mixing in the final N2 product, demonstrating that N2O does not react with other NO2− reduction intermediates; N2O reduction alone yielded only N2. In contrast, simultaneous catalytic reduction of 15NO2− and 14NO yielded mixed‐labeled 15/14N2 (MW: 29), whereas reduction of 15NO alone yields a mixture N2 and NH4+, the ratio of which varies with initial 15NO concentration. These findings, along with those from a new kinetic model we propose, indicate that highly reactive adsorbed NO (NO*), or other unspecified adsorbed N species (Nads), is a key intermediate involved in determining final product selectivity.

Enhancement of oxyanion and diatrizoate reduction kinetics using selected azo dyes on Pd-based catalysts

Azo dyes are widespread pollutants and potential cocontaminants for nitrate; we evaluated their effect on catalytic reduction of a suite of oxyanions, diatrizoate, and N-nitrosodimethylamine (NDMA). The azo dye methyl orange significantly enhanced (less than or equal to a factor of 5.24) the catalytic reduction kinetics of nitrate, nitrite, bromate, perchlorate, chlorate, and diatrizoate with several different Pd-based catalysts; NDMA reduction was not enhanced. Nitrate was selected as a probe contaminant, and a variety of azo dyes (methyl orange, methyl red, fast yellow AB, metanil yellow, acid orange 7, congo red, eriochrome black T, acid red 27, acid yellow 11, and acid yellow 17) were evaluated for their ability to enhance reduction. Hydrogenation energies of azo dyes were calculated using density functional theory and a volcano relationship between hydrogenation energies and reduction rate enhancement was observed. A kinetic model based on Brønsted-Evans-Polanyi (BEP) theory matched the volcano relationship and suggests sorbed azo dyes enhance reduction kinetics through hydrogen atom shuttling between reduced azo dyes (i.e., hydrazo dyes) and oxyanions or diatrizoate. This is the first research that has identified this synergetic effect, and it has implications for designing more efficient catalysts and reducing Pd costs in water treatment systems.

Enhancement of Nitrite Reduction Kinetics on Electrospun Pd-Carbon Nanomaterial Catalysts for Water Purification

We report a facile synthesis method for carbon nanofiber (CNF) supported Pd catalysts via one-pot electrospinning and their application for nitrite hydrogenation. A mixture of Pd acetylacetonate (Pd(acac)2), polyacrylonitrile (PAN), and nonfunctionalized multiwalled carbon nanotubes (MWCNTs) was electrospun and thermally treated to produce Pd/CNF-MWCNT catalysts. The addition of MWCNTs with a mass loading of 1.0-2.5 wt % (to PAN) significantly improved nitrite reduction activity compared to the catalyst without MWCNT addition. The results of CO chemisorption confirmed that the addition of MWCNTs increased Pd exposure on CNFs and hence improved catalytic activity.

Effects of anodic oxidation of a substoichiometric titanium dioxide reactive electrochemical membrane on algal cell destabilization and lipid extraction.

Efficient algal harvesting, cell pretreatment and lipid extraction are the major steps challenging the algal biofuel industrialization. To develop sustainable solutions for economically viable algal biofuels, our research aims at devising innovative reactive electrochemical membrane (REM) filtration systems for simultaneous algal harvesting and pretreatment for lipid extraction. The results in this work particularly demonstrated the use of the Ti4O7-based REM in algal pretreatment and the positive impacts on lipid extraction. After REM treatment, algal cells exhibited significant disruption in morphology and photosynthetic activity due to the anodic oxidation. Cell lysis was evidenced by the changes of fluorescent patterns of dissolved organic matter (DOM) in the treated algal suspension. The lipid extraction efficiency increased from 15.2 ± 0.6 g-lipidg-algae(-1) for untreated algae to 23.4 ± 0.7 g-lipidg-algae(-1) for treated algae (p<0.05), which highlights the potential to couple algal harvesting with cell pretreatment in an integrated REM filtration process.

Graphitic Carbon Nitride Supported Ultrafine Pd and Pd–Cu Catalysts: Enhanced Reactivity, Selectivity, and Longevity for Nitrite and Nitrate Hydrogenation

Novel Pd-based catalysts (i.e., Pd and Pd-Cu) supported on graphitic carbon nitride (g-C3N4) were prepared for nitrite and nitrate hydrogenation. The catalysts prepared by ethylene glycol reduction exhibited ultrafine Pd and Pd-Cu nanoparticles (∼2 nm), and they showed high reactivity, high selectivity toward nitrogen gas over byproduct ammonium, and excellent stability over multiple reaction cycles. The unique nitrogen-abundant surface, porous structure, and hydrophilic nature of g-C3N4 facilitates metal nanoparticle dispersion, mass transfer of reactants, and nitrogen coupling for nitrogen gas production to improve catalytic performance.

Enhanced Neural Stem Cell Functions in Conductive Annealed Carbon Nanofibrous Scaffolds with Electrical Stimulation.

Carbon-based nanomaterials have shown great promise in regenerative medicine because of their unique electrical, mechanical, and biological properties; however, it is still difficult to engineer 2D pure carbon nanomaterials into a 3D scaffold while maintaining its structural integrity. In the present study, we developed novel carbon nanofibrous scaffolds by annealing electrospun mats at elevated temperature. The resultant scaffold showed a cohesive structure and excellent mechanical flexibility. The graphitic structure generated by annealing renders superior electrical conductivity to the carbon nanofibrous scaffold. By integrating the conductive scaffold with biphasic electrical stimulation, neural stem cell proliferation was promoted associating with upregulated neuronal gene expression level and increased microtubule-associated protein 2 immunofluorescence, demonstrating an improved neuronal differentiation and maturation. The findings suggest that the integration of the conducting carbon nanofibrous scaffold and electrical stimulation may pave a new avenue for neural tissue regeneration.

Research highlights: functions of the drinking water microbiome - from treatment to tap

Maintaining drinking water safety from treatment to point-of use is a critical health priority. Growth and proliferation of opportunistic pathogens in premise plumbing is a well-known concern that can be mitigated by controlling water heater temperatures and water stagnation patterns. However, there is growing evidence that upstream processes, beginning with choice of treatment methods, have significant influences on premise plumbing microbial communities. Here, we highlight four papers that explore the roles of microbial communities in drinking water quality, and how design and treatment choices shape these roles.

Graphitic carbon nitride (g-C3N4)-based photocatalysts for water disinfection and microbial control: A review

Microbial contamination in drinking water is of great concern around the world because of high pathogenic risks to humans. Semiconductor photocatalysis has aroused an increasing interest as a promising environmental remediation technology for water disinfection and microbial control. Among various photocatalysts, graphitic carbon nitride (g-C3N4), as a fascinating two-dimensional conjugated polymer consisting of low-cost, earth-abundant elements, has drawn broad attention as a robust, metal-free, and visible-light-active material in the fields of both environmental remediation and solar energy conversion. Photocatalytic applications of g-C3N4-based nanomaterials for water splitting, hydrogen production, carbon dioxide reduction, and pollutant degradation have been extensively investigated and systematically reviewed. In contrast, their antimicrobial properties have been explored more recently due to the complex structure and unique metabolism of living microorganisms compared with chemicals. The corresponding rapidly increasing research efforts in the last five years have inspired us to conduct the review. This review is the first to comprehensively summarize the progress in design and antimicrobial performance of g-C3N4-based photocatalysts for water disinfection and microbial control, involving not only bacteria but also viruses and microalgae. Moreover, the underlying inactivation mechanisms of photocatalysts for microorganisms are evaluated to provide further understanding of g-C3N4-based advanced disinfection processes. In addition, some exciting future opportunities and challenges at the forefront of this research platform are pointed out. It is expected that this review can pave a new avenue for the development of a facile, cost-effective, environmental-friendly, and sustainable disinfection alternative.