Catalyst Design and Comparison

40 lessons, pages 4201–4240.

  1. Catalyst Design: Defining the Target — Activity, selectivity, lifetime and process constraints as distinct design objectives
  2. From Mechanism to Catalyst Descriptor — Choosing measurable or computable variables linked to a rate-controlling step
  3. The Sabatier Principle — Why adsorption that is too weak or too strong can both suppress turnover
  4. Volcano Plots as Structure–Activity Maps — Constructing and interpreting an activity maximum against a binding-energy descriptor
  5. Limits of a One-Descriptor Volcano — Changing mechanisms, coverage and transport that break a simple ranking
  6. Scaling Relations Between Adsorbates — Correlated binding energies and constraints on independent intermediate optimization
  7. Breaking Scaling Relations — Bifunctional sites, ensemble effects and stabilizing transition states selectively
  8. Adsorption Energies and Reference States — Consistent gas, solution and surface reference definitions for catalyst comparison
  9. Coverage-Dependent Catalysis — Site blocking, lateral interactions and changes in apparent rate with surface population
  10. Microkinetic Models — Combining elementary rates and site balances to predict turnover
  11. Degree of Rate Control — Sensitivity of overall rate to an elementary barrier or intermediate stability
  12. Rate-Determining Step: Use and Limits — Why a single slowest-step label can miss distributed kinetic control
  13. Catalyst Selectivity from Competing Paths — Branching barriers, intermediate coverage and product desorption
  14. Chemoselectivity, Regioselectivity and Stereoselectivity — Different product-selection questions in homogeneous catalysis
  15. Ligand Electronic Effects — Donation and back-donation as controls on organometallic elementary steps
  16. Ligand Steric Effects — Crowding, bite angle and accessible coordination environments
  17. Oxidative Addition and Reductive Elimination Design — Matching metal and ligand properties to bond activation and product release
  18. Migratory Insertion and Beta-Hydride Elimination — Controlling productive coupling versus competing organometallic pathways
  19. Homogeneous Catalyst Resting States — Identifying dominant observable species without confusing them with the active state
  20. Heterogeneous Active Sites — Terraces, edges, defects and support interfaces as distinct catalytic environments
  21. Nanoparticle Size and Ensemble Effects — Changing coordination and site distributions as catalyst particles shrink
  22. Single-Atom Catalysts — Isolated metal sites, support coordination and evidence needed for site identity
  23. Catalyst Supports and Metal–Support Interactions — Charge transfer, dispersion, anchoring and support participation in chemistry
  24. Acid–Base Catalysis on Solids — Brønsted and Lewis sites, strength distributions and probe reactions
  25. Electrocatalyst Potential and pH Effects — Potential-dependent intermediates, proton activity and consistent reference scales
  26. Oxygen Electrocatalysis Descriptors — Adsorbed oxygen intermediates, scaling and selectivity between pathways
  27. Hydrogen Evolution Catalyst Comparison — Hydrogen binding, water activation and interpreting measured overpotentials
  28. Carbon Dioxide Reduction Selectivity — Competition between carbon products and hydrogen evolution at an electrode
  29. Photocatalyst Band Alignment — Absorption, charge separation and redox driving forces in light-driven catalysts
  30. Enzyme-Inspired Catalyst Design — Second-sphere effects, proton relays and substrate positioning
  31. Turnover Number and Turnover Frequency — Defining active-site counts and comparing productivity without misleading normalization
  32. Kinetic Measurements for Catalysts — Initial rates, differential conditions and tests for transport limitation
  33. Operando Catalyst Characterization — Following structure and oxidation state under real reaction conditions
  34. Catalyst Deactivation Pathways — Poisoning, sintering, leaching, coking and structural transformation
  35. Stability Tests and Lifetime Claims — Time-on-stream, cycling and separating genuine stability from changing conditions
  36. Catalyst Regeneration and Recycling — Restoring activity and testing whether a reused material remains the same catalyst
  37. Fair Catalyst Benchmarking — Common protocols, product analysis, area normalization and uncertainty
  38. Data-Driven Catalyst Screening — Descriptors, training domains and experimental validation of model predictions
  39. Catalyst Selection for a Process — Balancing selectivity, rate, durability, cost and separation needs
  40. Catalyst Design and Comparison: Unit Review — Integrating mechanisms, descriptors, measurements and practical constraints