Wenqing Xu

All Publications

• Activity and Reactivity of Pyrogenic Carbonaceous Matter toward Organic Compounds. Environmental science & technology Pignatello, J. J., Mitch, W. A., Xu, W. 2017; 51 (16): 8893-8908

  Abstract

  Pyrogenic carbonaceous matter (PCM) includes environmental black carbon (fossil fuel soot, biomass char), engineered carbons (biochar, activated carbon), and related materials like graphene and nanotubes. These materials contact organic pollutants due to their widespread presence in the environment or through their use in various engineering applications. This review covers recent advances in our understanding of adsorption and chemical reactions mediated by PCM and the links between these processes. It also covers adsorptive processes previously receiving little attention and ignored in models such as steric constraints, physicochemical effects of confinement in nanopores, π interactions of aromatic compounds with polyaromatic surfaces, and very strong hydrogen bonding of ionizable compounds with surface functional groups. Although previous research has regarded carbons merely as passive sorbents, recent studies show that PCM can promote chemical reactions of sorbed contaminants at ordinary temperature, including long-range electron conduction between molecules and between microbes and molecules, local redox reactions between molecules, and hydrolysis. PCM may itself contain redox-active functional groups that are capable of oxidizing or reducing organic compounds and of generating reactive oxygen species (ROS) from oxygen, peroxides, or ozone. Amorphous carbons contain persistent free radicals that may play a role in observed redox reactions and ROS generation. Reactions mediated by PCM can impact the biogeochemical fate of pollutants and lead to useful strategies for remediation.

  View details for DOI 10.1021/acs.est.7b01088

  View details for PubMedID 28753285

• Reduction of Nitroaromatics Sorbed to Black Carbon by Direct Reaction with Sorbed Sulfides ENVIRONMENTAL SCIENCE & TECHNOLOGY Xu, W., Pignatello, J. J., Mitch, W. A. 2015; 49 (6): 3419-3426

  Abstract

  Sorption to black carbons is an important sink for organic contaminants in sediments. Previous research has suggested that black carbons (graphite, activated carbon, and biochar) mediate the degradation of nitrated compounds by sulfides by at least two different pathways: reduction involving electron transfer from sulfides through conductive carbon regions to the target contaminant (nitroglycerin) and degradation by sulfur-based intermediates formed by sulfide oxidation (RDX). In this study, we evaluated the applicability of black carbon-mediated reactions to a wider variety of contaminant structures, including nitrated and halogenated aromatic compounds, halogenated heterocyclic aromatic compounds, and halogenated alkanes. Among these compounds, black carbon-mediated transformation by sulfides over a 3-day time scale was limited to nitroaromatic compounds. The reaction for a series of substituted nitroaromatics proceeded by reduction, as indicated by formation of 3-bromoaniline from 3-bromonitrobenzene, and inverse correlation of log kobs with energy of the lowest unoccupied molecular orbital (ELUMO). The log kobs was correlated with sorbed sulfide concentration, but no reduction of 3-bromonitrobenzene was observed in the presence of graphite and sulfite, thiosulfate, or polysulfides. Whereas nitroglycerin reduction occurred in an electrochemical cell containing sheet graphite electrodes in which the reagents were placed in separate compartments, nitroaromatic reduction only occurred when sulfides were present in the same compartment. The results suggest that black carbon-mediated reduction of sorbed nitroaromatics by sulfides involves electron transfer directly from sorbed sulfides rather than transfer of electrons through conductive carbon regions. The existence of three different reaction pathways suggests a complexity to the sulfide-carbon system compared to the iron-carbon system, where contaminants are reduced by electron transfer through conductive carbon regions.

  View details for DOI 10.1021/es5045198

  View details for Web of Science ID 000351324400019

  View details for PubMedID 25671390

• Use of pyrogenic carbonaceous materials for the in situ, abiotic destruction of sediment-associated hydrophobic organic compounds with hydrogen sulfide Xu, W., Pignatello, J. J., Mitch, W. A. AMER CHEMICAL SOC. 2014

  View details for Web of Science ID 000349165105510