RESEARCH REVIEW · 4 NOVEMBER 2026

Alkali modification and neutralization of support acid sites

25 distinct research papers on alumina, silica–alumina and zeolites, including direct poisoning studies and explicitly marked related evidence.

What matters most

  1. Closest K/alumina starting point: Montanari et al. characterize potassium-doped alumina by IR and TPD [2]. The Cortéz study compares poisoning by alkali metals on γ-alumina [1].
  2. Hydroxide precedent: NaOH-modified γ-alumina has been tested in 3-pentanol conversion [16], while NaOH poisoning of silica–alumina acid sites was followed directly by pyridine IR [7]. These are NaOH, not evidence that KOH necessarily behaves identically.
  3. Direct HDO precedent: sulfided NiMo and CoMo on K-modified alumina were studied for guaiacol HDO; the study also reports changes to metal species [25].
  4. Do not equate lower acidity with the sole cause of catalytic change: potassium can also modify metal sites, reducibility, surface area, and basicity; zeolite base treatment may alter the framework and transport [4,9,22].

Applying the literature to a catalyst screen

Proposed, not a published protocol: compare the same untreated alumina with a reagent-solvent blank and several measured alkali loadings; keep drying, calcination and any metal deposition sequence identical where feasible. Include a KOH series and, if practical, a potassium-salt counterion control. The choice of nominal loading must be adapted to measured acid-site density and support stability.

Measure K uptake/leaching and surface area, and use matched-state pyridine IR to distinguish accessible Lewis and Brønsted acidity; temperature-resolved NH₃-TPD can complement it but cannot by itself distinguish those site types. CO₂ adsorption/TPD can assess basicity separately. Include a support-only and a complete-catalyst series to identify metal–promoter confounding [2,4,7,9]. Compare product yield, selectivity, stability and mass balance—not conversion alone.

Key reporting details: precursor identity and counterion; loading basis and actual K content; impregnation method and solution pH; calcination/reduction atmosphere and temperature; support phase; acidity measurement pretreatment; and whether any apparent change is normalized per gram or area. Strong alkaline solutions may also alter oxide structure, making matched controls essential.

Paper-by-paper evidence

Ordered by relevance, not by citation count. DOI links lead to publisher records; full text may be restricted. Descriptions are bounded by the evidence levels shown.

Direct · bare alumina

1. Study of the poisoning of γ‐Al2O3 by alkali metals addition

Gilberto Garcia Cortez, Sergio Rubén de Miguel, Osvaldo Antonio Scelza et al. · 1992 · Journal of Chemical Technology & Biotechnology

Alkali poisoning of γ-alumina was studied using acidity and isopropanol dehydration. The reported poisoning depends on the alkali cation and affects the acid-strength distribution. DOI: 10.1002/jctb.280530212

Evidence accessed: Abstract. Verify full experimental details before implementation.
Direct · K/alumina

2. Basic catalysis and catalysis assisted by basicity: FT-IR and TPD characterization of potassium-doped alumina

Tania Montanari, L. Castoldi, Luca Lietti et al. · 2011 · Applied Catalysis A General

FTIR and temperature-programmed desorption characterize potassium-doped alumina. A priority source for comparing surface acidity and basicity; accessible information did not establish a quantitative neutralization fraction. DOI: 10.1016/j.apcata.2011.04.016

Evidence accessed: Abstract. Verify full experimental details before implementation.
Supported catalyst · confounded

3. ACID-BASE PROPERTIES OF ALKALI PROMOTED CHROMIA-ALUMINA CATALYSTS

Jean P Damon, Paul O Scokart · 1980 · Chemistry Letters

Alkali promotion of chromia–alumina was studied by IR probes; the authors report elimination of Lewis acidity and increasing basic-site strength along the alkali series. Chromia complicates attribution to bare alumina. DOI: 10.1246/cl.1980.327

Evidence accessed: Abstract. Verify full experimental details before implementation.
Supported catalyst · confounded

4. Effects of potassium addition on the acidity and reducibility of chromia/alumina dehydrogenation catalysts

Elisabetta Rombi, Maria Giorgia Cutrufello, V. Solinas et al. · 2003 · Applied Catalysis A General

Study of potassium addition, acidity and reducibility of chromia/alumina; changes in the metal oxide and support cannot automatically be separated. DOI: 10.1016/S0926-860X(03)00308-9

Evidence accessed: Abstract. Verify full experimental details before implementation.
Adjacent · preparation

5. Interfacial chemistry in the preparation of catalytic potassium-modified aluminas

Alexandra Raluca Iordan, Mohamed I. Zaki, Charles J. Kappenstein · 1993 · Journal of the Chemical Society Faraday Transactions

Studies the interfacial chemistry of preparing potassium-modified alumina from potassium carbonate. Useful for impregnation and activation, but not by itself proof of quantitative acid-site neutralization. DOI: 10.1039/FT9938902527

Evidence accessed: Abstract. Verify full experimental details before implementation.
Adjacent · basicity

6. Synthesis and characterization of potassium-modified alumina superbases

Ying Wang, Jian Hua Zhu, Wen Yu Huang · 2001 · Physical Chemistry Chemical Physics

Examines synthesis and characterization of potassium-modified alumina superbases using carbonate/bicarbonate precursors. Increased basicity is not equivalent to a measured loss of a specific acid-site population. DOI: 10.1039/B100084P

Evidence accessed: Abstract. Verify full experimental details before implementation.
Direct · NaOH/silica–alumina

7. An Infrared Study of Acid Sites on Silica-Alumina Catalysts Poisoned with Sodium Hydroxide

Jun-ichiro Take, Toshiaki Ueda, Yukio Yoneda · 1978 · Bulletin of the Chemical Society of Japan

Pyridine IR examines acid sites after NaOH poisoning. Both Lewis and Brønsted site populations are affected; the study differentiates site type and apparent strength. DOI: 10.1246/bcsj.51.1581

Evidence accessed: Publisher abstract. Verify full experimental details before implementation.
Supported catalyst · adjacent

8. Potassium-modified silica-supported vanadium oxide catalysts applied for propene epoxidation

Agnieszka Held, Jolanta Kowalska‐Kuś, Krystyna Nowinska et al. · 2017 · Journal of Catalysis

Potassium modification of silica-supported vanadium oxide and propene oxidation: a metal-oxide-containing catalyst, not bare support neutralization. DOI: 10.1016/j.jcat.2016.12.001

Evidence accessed: Abstract. Verify full experimental details before implementation.
Supported catalyst · K/alumina

9. The effect of potassium on the balance of metal–acid site in Pt/Al 2 O 3 catalysts and their n -hexane dehydrogenation performance

Jinwen Tao, Xiaoyu Li, Hui Yuan et al. · 2024 · New Journal of Chemistry

Increasing K content reduces acid sites and changes n-hexane dehydrogenation selectivity; it also changes the Pt function, preventing attribution of performance solely to acidity. DOI: 10.1039/D4NJ01967A

Evidence accessed: Publisher abstract. Verify full experimental details before implementation.
Direct · Na/alumina

10. Effect of sodium ion impurities in γ-alumina on the catalytic, vapor-phase dehydration of ethyl alcohol

R.A. Ross, D. Bennett · 1967 · Journal of Catalysis

Studies the effect of sodium impurities in γ-alumina on ethanol dehydration, an acid-sensitive probe reaction. Sodium is an impurity rather than necessarily an added hydroxide. DOI: 10.1016/0021-9517(67)90318-1

Evidence accessed: Abstract. Verify full experimental details before implementation.
Direct · Na/alumina

11. Comparative study of the effects of sodium impurity and amorphisation on the Lewis acidity of γ- alumina

A. B. Mohammed Saad, V.A. Ivanov, J.C. Lavalley et al. · 1993 · Applied Catalysis A General

Compares sodium impurity and amorphization effects on γ-alumina Lewis acidity, using spectroscopic and reaction evidence. Structure and sodium must be disentangled. DOI: 10.1016/0926-860X(93)80046-S

Evidence accessed: Abstract. Verify full experimental details before implementation.
Direct · Na/alumina

12. The role of sodium and structure on the catalytic behavior of alumina: I. Isopropanol dehydration activity

Swaminathan T. Srinivasan, C.R. Narayanan, Andrew Biaglow et al. · 1995 · Applied Catalysis A General

For one γ-alumina, the abstract reports that 400 ppm Na reduced isopropanol dehydration reactivity by 75%. This is a rate/activity change, not a direct 75% site count. DOI: 10.1016/0926-860X(95)00161-1

Evidence accessed: Abstract. Verify full experimental details before implementation.
Direct · Na/alumina

13. The role of sodium and structure on the catalytic behavior of alumina: II. IR spectroscopy

Swaminathan T. Srinivasan, C.R. Narayanan, Abhaya K. Datye · 1995 · Applied Catalysis A General

IR spectroscopy companion to the preceding study: examines surface hydroxyl groups and sodium/structure effects on acidity. The accessible record does not establish a numerical site loss. DOI: 10.1016/0926-860X(95)00162-X

Evidence accessed: Abstract / metadata. Verify full experimental details before implementation.
Adjacent · Na/alumina

14. Effect of sodium oxide on the morphology and basicity of alumina

V.A. Ivanov, Anne Pieplu, J.C. Lavalley et al. · 1995 · Applied Catalysis A General

Examines how sodium oxide affects alumina morphology and basicity. Useful for distinguishing structural and basicity changes from acid-site measurements. DOI: 10.1016/0926-860X(95)00149-2

Evidence accessed: Abstract / metadata. Verify full experimental details before implementation.
Supported catalyst · NiMo

15. Hydrofining activity and acid–base properties of nickel–molybdenum catalysts incorporated on sodium and magnesium ions-modified alumina

Marek Lewandowski, Zenon Sarbak · 1998 · Applied Catalysis A General

Examines Ni–Mo catalysts on sodium- and magnesium-modified alumina and their acid–base and hydrofining behavior. Metal phase effects are a major confounder. DOI: 10.1016/S0926-860X(97)00354-2

Evidence accessed: Abstract. Verify full experimental details before implementation.
Direct · NaOH/alumina

16. Catalytic activity and selectivity of NaOH-doped γ-aluminas. Dehydration and dehydrogenation of 3-pentanol

T. T. Chuang, Ivo G. Dalla Lana · 1972 · Journal of the Chemical Society Faraday Transactions 1 Physical Chemistry in Condensed Phases

Studies catalytic activity and selectivity of NaOH-doped γ-aluminas using 3-pentanol dehydration and dehydrogenation. Detailed doses and site measurements require the full paper. DOI: 10.1039/F19726800773

Evidence accessed: Metadata / abstract. Verify full experimental details before implementation.
Direct · Na/alumina

17. Acidity, cumene conversion and thiophene hydrodesulfurization over alumina and surface modified aluminas

Zenon Sarbak · 1997 · Applied Catalysis A General

Compares untreated and surface-modified aluminas by IR probe molecules and reactions. The sodium-modified sample is reported to have fewer and weaker Lewis sites; catalytic response depends on the reaction. DOI: 10.1016/S0926-860X(97)00061-6

Evidence accessed: Institutional abstract. Verify full experimental details before implementation.
Supported catalyst · Na/silica–alumina

18. The activity of nickel on sodium-neutralized silica-alumina

C HUANG · 1978 · Journal of Catalysis

Ni on sodium-neutralized silica–alumina: support acidity falls and acid-catalyzed cumene dealkylation decreases with Na; compare metal properties before assigning all changes to acidity. DOI: 10.1016/0021-9517(78)90147-1

Evidence accessed: Repository abstract. Verify full experimental details before implementation.
Direct · silica–alumina

19. Effects of metal acetate salts on the catalytic cracking of cumene over silica-alumina

T. Fort · 1968 · Journal of Catalysis

Metal acetate salts poison cumene cracking over silica–alumina. Cation identity and loading matter; chemical neutralization and blocking are potential competing explanations. DOI: 10.1016/0021-9517(68)90016-X

Evidence accessed: Abstract. Verify full experimental details before implementation.
Adjacent · support comparison

20. Modification of acid–base properties of alkali metals containing catalysts by the application of various supports

Vanesa Calvino Casilda, Rosa María Martín Aranda, Izabela Sobczak et al. · 2006 · Applied Catalysis A General

Alkali acetates on silica, alumina and niobia are compared using acid–base probe reactions. Basicity responses vary with support; generating basicity does not itself quantify acidity loss. DOI: 10.1016/j.apcata.2006.02.013

Evidence accessed: Abstract. Verify full experimental details before implementation.
Adjacent · support comparison

21. Catalytic properties of alkali metal-modified oxide supports for the Knoevenagel condensation: Kinetic aspects

Vanesa Calvino Casilda, Rosa María Martín Aranda, Antonio José López-Peinado et al. · 2008 · Catalysis Today

Compares alkali-modified oxide supports in Knoevenagel condensation and kinetics; provides complementary basic-catalysis context rather than direct proof of alumina site neutralization. DOI: 10.1016/j.cattod.2008.08.023

Evidence accessed: Abstract. Verify full experimental details before implementation.
Adjacent · zeolite desilication

22. Alkali-treatment technique — new method for modification of structural and acid-catalytic properties of ZSM-5 zeolites

Masaru Ogura, Shin‐ya Shinomiya, Junko Tateno et al. · 2001 · Applied Catalysis A General

NaOH treatment of ZSM-5 modifies porosity and acidity; the subsequent H-form exchange means the treated material is not simply a sodium-neutralized catalyst. Transport and framework changes confound activity comparisons. DOI: 10.1016/S0926-860X(01)00645-7

Evidence accessed: Article/abstract. Verify full experimental details before implementation.
Adjacent · zeolite desilication

23. Gas phase glycerol dehydration over H-ZSM-5 zeolite modified by alkaline treatment with Na2CO3

C.D. Lago, H.P. Decolatti, Lucas Tonutti et al. · 2018 · Journal of Catalysis

Na₂CO₃-treated H-ZSM-5 was examined for glycerol dehydration. Desilication, exchange and porosity changes distinguish this from a clean alkali-neutralization experiment. DOI: 10.1016/j.jcat.2018.07.036

Evidence accessed: Abstract. Verify full experimental details before implementation.
Direct · zeolite neutralization

24. Acidity tuning of HZSM-5 zeolite by neutralization titration for coke inhibition in supercritical catalytic cracking of n-dodecane

Xiaochao Xian, Mengjun He, Yakai Gao et al. · 2021 · Applied Catalysis A General

Acidity tuning of HZSM-5 by neutralization titration for coke inhibition in n-dodecane cracking. Verify titrant, loading and quantitative results in the full text before adopting a protocol. DOI: 10.1016/j.apcata.2021.118278

Evidence accessed: Abstract / metadata. Verify full experimental details before implementation.
HDO · K/γ-alumina-supported sulfides

25. Hydrodeoxygenation of guaiacol using NiMo and CoMo catalysts supported on alumina modified with potassium

Mora-Vergara and coauthors · 2018 · Catalysis Today 302, 125–135

Directly relevant to lignin-model HDO: sulfided NiMo and CoMo catalysts on K-modified γ-alumina were tested in a batch reactor at 523 K and reported hydrogen pressure of 5.5 MPa. Potassium decreased acidity and guaiacol conversion while shifting selectivity toward direct aromatic C–OH bond scission and hydrogenation. It also changed Mo coordination and increased the relative concentration of inactive NiAl₂O₄ and CoAl₂O₄ species. Thus the reaction outcome cannot be assigned to acidity alone; consult the paper for pressure basis and details. DOI: 10.1016/j.cattod.2017.07.015

Evidence accessed: institutional abstract; full experimental tables were not reviewed.

Search scope and limitations

Search date: 4 November 2026. Discovery used scholarly and publisher records across potassium-doped alumina, sodium-poisoned alumina, hydroxide-treated silica–alumina, supported metal catalysts and alkaline-treated zeolites. DOI-to-title pairs were checked against OpenAlex metadata; where available, publisher or repository abstracts informed the evidence summaries. This is a relevance-selected, non-exhaustive review, not a systematic review or a full-text review of all 25 papers.

Paper labels identify whether the experiment directly involves the support or is a confounded/adjacent comparison. “Direct” identifies relevance of the material or neutralization test, not proof of a unique atomic mechanism. Studies describing formation of basic sites or changes in activity are not treated as quantitative measurements of acid sites lost.