Abstract
Perchlorate (ClO4-) is a pervasive, harmful, and inert anion on both Earth and Mars. Current technologies for ClO4- reduction entail either harsh conditions or multicomponent enzymatic processes. Herein, we report a heterogeneous (L)Mo-Pd/C catalyst directly prepared from Na2MoO4, a bidentate nitrogen ligand (L), and Pd/C to reduce aqueous ClO4- into Cl- with 1 atm of H2 at room temperature. A suite of instrument characterizations and probing reactions suggest that the MoVI precursor and L at the optimal 1:1 ratio are transformed in situ into oligomeric MoIV active sites at the carbon-water interface. For each Mo site, the initial turnover frequency (TOF0) for oxygen atom transfer from ClOx- substrates reached 165 h-1. The turnover number (TON) reached 3840 after a single batch reduction of 100 mM ClO4-. This study provides a water-compatible, efficient, and robust catalyst to degrade and utilize ClO4- for water purification and space exploration.
| Original language | English |
|---|---|
| Pages (from-to) | 7891-7896 |
| Number of pages | 6 |
| Journal | Journal of the American Chemical Society |
| Volume | 143 |
| Issue number | 21 |
| DOIs | |
| State | Published - Jun 2 2021 |
| Externally published | Yes |
Funding
Dr. Krassimir Bozhilov assisted STEM characterization at the Central Facility for Advanced Microscopy and Microanalysis (CFAMM) at UC Riverside. Dr. Ich Tran assisted XPS characterization at the UC Irvine Materials Research Institute (IMRI). Funding: UC Riverside startup grant and the National Science Foundation (NSF) Division of Chemical, Bioengineering, Environmental, and Transport Systems, Environmental Engineering Program (CBET-1932942) for C.R., E.Y.B., J.G., J.P., and J.L.; the U.S. Department of Energy (DOE) Experimental Program to Stimulate Competitive Research (DOE-EPSCoR DE-SC0016272) for P.Y. and M.Z.; NSF Division of Chemistry, Chemical Catalysis Program (CHE-1566106) for J.S. and Y.W. The use of Stanford Synchrotron Radiation Lightsource at SLAC National Accelerator Laboratory was supported by the U.S. DOE, Office of Science, Office of Basic Energy Sciences (DE-AC02-76SF00515). The XPS facility at IMRI was funded in part by NSF Major Research Instrumentation Program (CHE- 1338173). Dr. Krassimir Bozhilov assisted STEM characterization at the Central Facility for Advanced Microscopy and Microanalysis (CFAMM) at UC Riverside. Dr. Ich Tran assisted XPS characterization at the UC Irvine Materials Research Institute (IMRI). Funding: UC Riverside startup grant and the National Science Foundation (NSF) Division of Chemical, Bioengineering, Environmental, and Transport Systems, Environmental Engineering Program (CBET-1932942) for C.R., E.Y.B., J.G., J.P., and J.L.; the U.S. Department of Energy (DOE) Experimental Program to Stimulate Competitive Research (DOE-EPSCoR DE-SC0016272) for P.Y. and M.Z.; NSF Division of Chemistry, Chemical Catalysis Program (CHE-1566106) for J.S. and Y.W. The use of Stanford Synchrotron Radiation Lightsource at SLAC National Accelerator Laboratory was supported by the U.S. DOE, Office of Science, Office of Basic Energy Sciences (DE-AC02-76SF00515). The XPS facility at IMRI was funded in part by NSF Major Research Instrumentation Program (CHE-1338173).
| Funders | Funder number |
|---|---|
| DOE-EPSCoR | DE-SC0016272, CHE-1566106 |
| Division of Chemical, Bioengineering, Environmental, and Transport Systems, Environmental Engineering Program | CBET-1932942 |
| National Science Foundation | |
| U.S. Department of Energy | |
| Office of Science | |
| Basic Energy Sciences | CHE-1338173, DE-AC02-76SF00515 |
| University of California, Riverside | |
| UC Irvine Materials Research Institute |