Operando Electronic Structure Engineering of Zhang–Rice Singlet Catalysts for Simultaneous Water Oxidation and Volatile Organic Compound Mitigation in Urban Transportation Microenvironments

Abstract

The urban transportation microenvironment constitutes a pervasive and underexplored exposure landscape for volatile organic compounds (VOCs), with subways, buses, and taxis exhibiting distinct chemical fingerprints and adverse health outcomes. Simultaneously, electrochemical water oxidation driven by earth-abundant catalysts offers a pathway toward decentralized oxygen generation and coupled pollutant degradation, yet catalysts capable of performing both functions with high efficiency under realistic, fluctuating conditions remain elusive. This paper advances a systems-level framework for operando electronic structure engineering of Zhang–Rice singlet (ZRS) catalysts to achieve concurrent oxygen evolution reaction (OER) and VOC mineralization within vehicular microenvironments. The ZRS, a correlated quantum state arising from hole coupling between copper 3d and oxygen 2p orbitals, has recently been demonstrated as a powerful motif for triggering water oxidation under operando conditions. We argue that external stimuli such as applied bias, illumination, and humidity can dynamically modulate the ZRS formation energy and hole delocalization, thereby tuning both OER selectivity and the complete oxidation of aromatic and aliphatic VOCs. Moving beyond molecular-scale optimization, the article examines structural trade-offs embedded in the design of catalytic modules for integration across heterogeneous vehicle fleets—including energy supply architecture, real-time feedback control through environmental sensing, modular cartridge-based replacement systems, and communications protocols with vehicle climate control units. Detailed analysis addresses robustness against poisoning, thermal cycling, and mechanical vibration, as well as sustainability through reliance on copper-based oxides that circumvent critical raw material bottlenecks. Governance, fairness, and policy dimensions are explored from the perspective of differentiated exposure burdens across socioeconomic strata and the need for regulatory frameworks that encourage equitable deployment of advanced catalytic air purification in both private and public transit. The study ultimately outlines a socio-technical roadmap in which operando electronic structure engineering converges with distributed infrastructure thinking to transform urban mobility into a site of active environmental remediation.