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Rapid dechlorination and full mineralization of para-chlorophenol (4-CP), a toxic contaminant, are unfulfilled goals in water treatment. Means to achieve both goals stem from the novel concept of coupling catalysis by palladium nanoparticles (PdNPs) with biodegradation in a biofilm. Here, we demonstrate that a synergistic version of the hydrogen (H 2 )-based membrane biofilm reactor (MBfR) enabled simultaneous removals of 4-CP and cocontaminating nitrate. In situ generation of PdNPs within the MBfR biofilm led to rapid 4-CP reductive dechlorination, with >90% selectivity to more bioavailable cyclohexanone. Then, the biofilm mineralized the cyclohexanone by utilizing it as a supplementary electron donor to accelerate nitrate reduction. Long-term operation of the Pd-MBfR enriched the microbial community in cyclohexanone degraders within Clostridium, Chryseobacterium, and Brachymonas. In addition, the PdNP played an important role in accelerating nitrite reduction; while NO 3 − reduction to NO 2 − was entirely accomplished by bacteria, NO 2 − reduction to N 2 was catalyzed by PdNPs and bacterial reductases. This study documents a promising option for efficient and complete remediation of halogenated organics and nitrate by the combined action of PdNP and bacterial catalysis.

Per- and polyfluoroalkyl substances (PFASs) comprise a group of widespread and recalcitrant contaminants that are attracting increasing concern due to their persistence and adverse health effects. This study evaluated removal of one of the most prevalent PFAS, perfluorooctanoic acid (PFOA), in H2-based membrane catalyst-film reactors (H2-MCfRs) coated with palladium nanoparticles (Pd0NPs). Batch tests documented that Pd0NPs catalyzed hydrodefluorination of PFOA to partially fluorinated and nonfluorinated octanoic acids; the first-order rate constant for PFOA removal was 0.030 h–1, and a maximum defluorination rate was 16 μM/h in our bench-scale MCfR. Continuous-flow tests achieved stable long-term depletion of PFOA to below the EPA health advisory level (70 ng/L) for up to 70 days without catalyst loss or deactivation. Two distinct mechanisms for Pd0-based PFOA removal were identified based on insights from experimental results and density functional theory (DFT) calculations: (1) nonreactive chemisorption of PFOA in a perpendicular orientation on empty metallic surface sites and (2) reactive defluorination promoted by physiosorption of PFOA in a parallel orientation above surface sites populated with activated hydrogen atoms (Hads *). Pd0-based catalytic reduction chemistry and continuous-flow treatment may be broadly applicable to the ambient-temperature destruction of other PFAS compounds.

Scalable applications of precious-metal catalysts for water treatment face obstacles in H2-transfer efficiency and catalyst stability during continuous operation. Here, we introduce a H2-based membrane catalyst-film reactor (H2-MCfR), which enables in situ reduction and immobilization of a film of heterogeneous Pd0 catalysts that are stably anchored on the exterior of a nonporous H2-transfer membrane under ambient conditions. In situ immobilization had >95% yield of Pd0 in controllable forms, from isolated single atoms to moderately agglomerated nanoparticles (averaging 3–4 nm). A series of batch tests documented rapid Pd-catalyzed reduction of a wide spectrum of oxyanions (nonmetal and metal) and organics (e.g., industrial raw materials, solvents, refrigerants, and explosives) at room temperature, owing to accurately controlled H2 supply on demand. Reduction kinetics and selectivity were readily controlled through the Pd0 loading on the membranes, H2 pressure, and pH. A 45-day continuous treatment of trichloroethene (TCE)-contaminated water documented removal fluxes up to 120 mg-TCE/m2/d with over 90% selectivity to ethane and minimal (<1.5%) catalyst leaching or deactivation. The results support that the H2-MCfR is a potentially sustainable and reliable catalytic platform for reducing oxidized water contaminants: simple synthesis of an active and versatile catalyst that has long-term stability during continuous operation.

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PFAAs (perfluorinated alkyl acids) have become a concern because of their widespread pollution and persistence. A previous study introduced a novel approach for removing and hydrodefluorinating perfluorooctanoic acid (PFOA) using palladium nanoparticles (Pd 0 NPs) in situ synthesized on H 2 -gas-transfer membranes. This work focuses on the products, pathways, and optimal catalyst conditions. Kinetic tests tracking PFOA removal, F − release, and hydrodefluorination intermediates documented that PFOA was hydrodefluorinated by a mixture of parallel and stepwise reactions on the Pd 0 NP surfaces. Slow desorption of defluorination products lowered the catalyst's activity for hydrodefluorination. Of the platinum group metals studied, Pd was overall superior to Pt, Rh, and Ru for hydrodefluorinating PFOA. pH had a strong influence on performance: PFOA was more strongly adsorbed at higher pH, but lower pH promoted defluorination. A membrane catalyst-film reactor (MCfR), containing an optimum loading of 1.2 g/m 2 Pd 0 for a total Pd amount of 22 mg, removed 3 mg/L PFOA during continuous flow for 90 days, and the removal flux was as high as 4 mg PFOA/m 2 /d at a steady state. The EPA health advisory level (70 ng/L) also was achieved over the 90 days with the influent PFOA at an environmentally relevant concentration of 500 ng/L. The results document a sustainable catalytic method for the detoxification of PFOA-contaminated water.

The MoS2 photodetector on different substrates stacked via van der Waals force has been explored extensively because of its great potential in optoelectronics. Here, we integrate multilayer MoS2 on monocrystalline SiC substrate though direct chemical vapor deposition. The MoS2 film on SiC substrate shows high quality and thermal stability, in which the full width at half-maximum and first-order temperature coefficient for the $E_{2g}^1$ Raman mode are 4.6 cm−1 and −0.01382 cm−1/K, respectively. The fabricated photodetector exhibits excellent performance in the UV and visible regions, including an extremely low dark current of ~1 nA at a bias of 20 V and a low noise equivalent of 10−13–10−15 W/Hz1/2. The maximum responsivity of the MoS2/SiC photodetector is 5.7 A/W with the incident light power of 4.35 μW at 365 nm (UV light). Furthermore, the maximum photoconductive gain, noise equivalent power, and normalized detectivity for the fabricated detector under 365 nm illumination are 79.8, 7.08 × 10−15 W/Hz1/2, and 3.07 × 1010 Jonesat, respectively. We thus demonstrate the possibility for integrating high-performance photodetectors array based on MoS2/SiC via direct chemical vapor growth.

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