{"doi":"10.1021/jacs.1c02835","title":"Spectroscopic Definition of a Highly Reactive Site in Cu-CHA for Selective Methane Oxidation: Tuning a Mono-μ-Oxo Dicopper(II) Active Site for Reactivity","abstract":"Using UV–vis and resonance Raman spectroscopy, we identify a [Cu2O]2+ active site in O2 and N2O activated Cu-CHA that reacts with methane to form methanol at low temperature. The Cu–O–Cu angle (120°) is smaller than that for the [Cu2O]2+ core on Cu-MFI (140°), and its coordination geometry to the zeolite lattice is different. Site-selective kinetics obtained by operando UV–vis show that the [Cu2O]2+ core on Cu-CHA is more reactive than the [Cu2O]2+ site in Cu-MFI. From DFT calculations, we find that the increased reactivity of Cu-CHA is a direct reflection of the strong [Cu2OH]2+ bond formed along the H atom abstraction reaction coordinate. A systematic evaluation of these [Cu2O]2+ cores reveals that the higher O–H bond strength in Cu-CHA is due to the relative orientation of the two planes of the coordinating bidentate O–Al–O T-sites that connect the [Cu2O]2+ core to the zeolite lattice. This work along with our earlier study ( J. Am. Chem. Soc, 2018, 140, 9236−9243) elucidates how zeolite lattice constraints can influence active site reactivity.","journal":"Journal of the American Chemical Society","year":2021,"id":151647,"datarank":0.0,"base_score":0.0,"endowment":0.0,"self_citation_contribution":0.0,"citation_network_contribution":0.0,"self_endowment_contribution":0.0,"citer_contribution":0.0,"corpus_percentile":null,"corpus_rank":null,"citation_count":81,"citer_count":0,"citers_with_citation_signal":0,"citers_with_endowment":0,"datacite_reuse_total":0,"is_dataset":false,"is_dataset_confidence":0.9474,"is_data_producer":false,"deposit_databanks":null,"is_oa":true,"file_count":0,"downloads":0,"has_version_chain":false,"published_date":"2021-01-01","fair_score":null,"fair_percentile":null,"algorithm_id":"datarank_citation_only_1hop_v6","ranking_scope":"data_only","authors":[{"id":644518,"name":"Dieter Plessers","orcid":"0000-0001-8906-8447","position":1,"is_corresponding":false},{"id":644519,"name":"Alexander J. Heyer","orcid":"0000-0003-4362-8191","position":2,"is_corresponding":false},{"id":644520,"name":"Max L. Bols","orcid":"0000-0002-4576-5969","position":3,"is_corresponding":false},{"id":644521,"name":"Robert A. Schoonheydt","orcid":"0000-0003-0891-773X","position":4,"is_corresponding":false},{"id":644522,"name":"Bert F. Sels","orcid":"0000-0001-9657-1710","position":5,"is_corresponding":false},{"id":271050,"name":"Edward I. Solomon","orcid":"0000-0003-0291-3199","position":6,"is_corresponding":false},{"id":644517,"name":"Hannah M. Rhoda","orcid":"0000-0001-5730-5209","position":0,"is_corresponding":true}],"reference_count":46,"raw_metadata":null,"created_at":"2026-07-18T23:43:16.823357Z","pmid":"33970624","pmcid":null,"fwci":null,"citation_percentile":null,"influential_citations":0,"oa_status":null,"license":null,"views":0,"total_file_size_bytes":0,"version_count":0,"fair_f":null,"fair_a":null,"fair_i":null,"fair_r":null,"fair_zscore":null,"fair_rationale":null,"fair_model":null,"fair_agent_version":null,"fair_fulltext_source":null,"fair_has_llm":null,"fair_computed_at":null,"clinical_trials":[],"software_tools":[],"db_accessions":[],"linked_datasets":[],"topics":[]}