The relationships among the macroscopic compositional parameters of a Cu-exchanged SSZ-13 zeolite catalyst, the types and numbers of Cu active sites, and activity for the selective catalytic reduction (SCR) of NOx with NH3 are established through experimental interrogation and computational analysis of materials across the catalyst composition space. Density functional theory, stochastic models, and experimental characterizations demonstrate that within the synthesis protocols applied here and across Si:Al ratios, the volumetric density of six-membered-rings (6MR) containing two Al (2Al sites) is consistent with a random Al siting in the SSZ-13 lattice subject to Löwenstein's rule. Further, exchanged Cu(II) ions first populate these 2Al sites before populating remaining unpaired, or 1Al, sites as Cu(II)OH. These sites are distinguished and enumerated ex situ through vibrational and X-ray absorption spectroscopies (XAS) and chemical titrations. In situ and operando XAS follow Cu oxidation state and coordination environment as a function of environmental conditions including low-temperature (473 K) SCR catalysis and are rationalized through first-principles thermodynamics and ab initio molecular dynamics. Experiment and theory together reveal that the Cu sites respond sensitively to exposure conditions, and in particular that Cu species are solvated and mobilized by NH3 under SCR conditions. While Cu sites are spectroscopically and chemically distinct away from these conditions, they exhibit similar turnover rates, apparent activation energies and apparent reaction orders at the SCR conditions, even on zeolite frameworks other than SSZ13.

Copper ions exchanged into zeolites are active for the selective catalytic reduction (SCR) of nitrogen oxides (NO ) with ammonia (NH), but the low-temperature rate dependence on copper (Cu) volumetric density is inconsistent with reaction at single sites. We combine steady-state and transient kinetic measurements, x-ray absorption spectroscopy, and first-principles calculations to demonstrate that under reaction conditions, mobilized Cu ions can travel through zeolite windows and form transient ion pairs that participate in an oxygen (O)-mediated Cu→Cu redox step integral to SCR. Electrostatic tethering to framework aluminum centers limits the volume that each ion can explore and thus its capacity to form an ion pair. The dynamic, reversible formation of multinuclear sites from mobilized single atoms represents a distinct phenomenon that falls outside the conventional boundaries of a heterogeneous or homogeneous catalyst.

Theory and experiment reveal relationships between observed UV-visible spectra and ion exchange site types, ion nuclearity, and finite-temperature dynamics in Cu exchanged chabazite (SSZ-13) zeolites.

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Electrochemistry has the potential to sustainably transform molecules with electrons supplied by renewable electricity. It is one of many solutions towards a more circular, sustainable and equitable society. To achieve this, collaboration between industry and research laboratories is a must. Atomistic understanding from fundamental experiments and modelling can be used to engineer optimized systems whereas limitations set by the scaled-up technology can direct the systems studied in the research laboratory. In this Primer, best practices to run clean laboratoryscale electrochemical systems and tips for the analysis of electrochemical data to improve accuracy and reproducibility are introduced. How characterization and modelling are indispensable in providing routes to garner further insights into atomistic and mechanistic details is discussed. Finally, important considerations regarding material and cell design for scaling up water electrolysis are highlighted and the role of hydrogen in our society's energy transition is discussed. The future of electrochemistry is bright and major breakthroughs will come with rigour and improvements in the collection, analysis, benchmarking and reporting of electrochemical water splitting data.