Evidence-screened literature comparison · 19 October 2026

NiMo vs Ni–VOx for lignin-phenolic HDO

What the published evidence can—and cannot—say about activity when the catalyst is hydrogen-reduced and non-sulfided. The requested threshold was at least seven papers per family; this review reports the verified shortfall rather than filling it with unrelated systems.

Bottom line: NiMo has several direct phenol/guaiacol HDO precedents, with reported high conversion and hydrocarbon/phenolic product yields depending strongly on support, reduction, and target pathway. For Ni–VOx, the search found one direct m-cresol study suggesting improved selective deoxygenation at a Ni–VOx interface. That is a promising hypothesis, not yet a replicated basis to rank NiVOx against NiMo. Seven qualifying papers were not verified for either catalyst family.
4direct NiMo / reduced-state papers screened; 3 with specific performance details available
1direct Ni–VOx phenolic-HDO paper located
0valid seven-paper-per-family comparisons in this evidence set

What “activity” means here

Conversion alone is not a fair activity ranking. The papers use different phenolics, supports, temperatures, hydrogen pressures, solvents/reactors, and product targets. A catalyst can consume the substrate but stop at phenol/cyclohexanol, or remove oxygen to aromatic/cycloalkane products; selectivity and yield therefore matter alongside conversion. No comparable rate/TOF dataset was established across NiMo and Ni–VOx.

Scope: direct HDO of lignin-derived phenolic model compounds; catalysts used in reduced/non-sulfided state. Sulfided-only results are excluded. Nitride/carbide catalysts and catalysts whose required H2-reduction state was not verified are kept out of the strict evidence count.

NiMo: direct reduced-state evidence

Kordouli et al. (2018) — phenol, Mo promotion and support

Direct; partially reduced

Hydrodeoxygenation of phenol on bifunctional Ni-based catalysts: Effects of Mo promotion and support. Applied Catalysis B: Environmental 238, 147–160.

At 310 °C and 3 MPa H2, Mo promotion increased reported phenol conversion by 18% on alumina and 38% on amorphous silica–alumina; the maximum conversion reported was 96% over Mo–Ni/ASA. Cyclohexane and cyclohexanol were principal products. This supports promotion under those specific conditions, not a universal NiMo ranking.

DOI: 10.1016/j.apcatb.2018.07.012 · Evidence: publisher-linked postprint/indexed record; full methods not independently audited for this summary.

Phan et al. (2020) — guaiacol, spray-pyrolysis NiMo/Al2O3–TiO2

Direct; reduced catalyst

Spray pyrolysis synthesis of bimetallic NiMo/Al2O3–TiO2 catalyst for hydrodeoxygenation of guaiacol: Effects of bimetallic composition and reduction temperature. Journal of Industrial and Engineering Chemistry 83, 351–358.

A 10 wt% Ni–20 wt% Mo formulation is reported at 98% conversion and 100% hydrocarbon selectivity (85% cyclohexane, 13% methylcyclohexane, 2% toluene), with 24 h stability reported. The paper explicitly investigates reduction temperature. These figures are study-specific and should not be compared directly with batch phenol studies.

DOI: 10.1016/j.jiec.2019.12.008 · Evidence: indexed/publisher record; detailed condition matching across studies not performed.

Adilina et al. (2019) — guaiacol on pillared clay

Direct; reduced and sulfided states compared

Hydrodeoxygenation of Guaiacol as a Bio-Oil Model Compound over Pillared Clay-Supported Nickel–Molybdenum Catalysts. The Journal of Physical Chemistry C 123, 21429–21439.

The H2-reduced NiMo-PILC was prepared at 773 K for 3 h and showed moderate activity at 623 K/20 bar, with a broad product distribution and some unidentified products. The same-study sulfided catalyst's complete conversion/77% phenol result is not evidence for the reduced catalyst and is intentionally not used to characterize reduced NiMo.

DOI: 10.1021/acs.jpcc.9b01890 · Evidence: abstract/indexed record; reduced-state outcome is qualitative in accessible summary.

Hydrodeoxygenation of Phenol Over Hydrotreatment Catalysts in their Reduced and Sulfided States (2014)

Direct state comparison; outcome detail limited

The Open Catalysis Journal 7, 18–31 (2014). Compares reduced and sulfided CoMo, NiMo and NiW catalysts on γ-Al2O3 and TiO2 for phenol HDO. This establishes a directly relevant catalyst-state comparison, but the accessible record did not provide enough NiMo-specific quantitative results for a ranking.

DOI: 10.2174/1876214X01407010018 · Evidence: bibliographic/indexed record; detailed outcome not independently reviewed.

NiMo count caveat: Four relevant reduced/reduced-versus-sulfided papers were screened, not seven. Several apparently attractive papers were excluded from the strict set: Ni–Mo nitride/carbide catalysts (different active phase) and MOF-derived NiMo carbon where a separate H2-reduction activation step was not confirmed in the accessible evidence. Sulfided performance was not counted as non-sulfided performance.

Ni–VOx: direct evidence and limits

Zhou et al. (2025) — Ni–VOx/SiO2 interface, m-cresol

Direct; non-sulfided reduced Ni–VOx

Efficient catalytic hydrodeoxygenation of lignin derived phenolics on Ni-VOx interface. CIESC Journal 76(12) (2025), 6366–6375.

The publisher abstract reports that Ni alone favors hydrogenation and C–C cleavage and gives low toluene selectivity; an appropriate VOx amount reduces Ni particle size, increases Ni–VOx interface density, and improves selective m-cresol conversion to toluene. Methylcyclohexanol probing is interpreted as supporting direct deoxygenation as the main route. H2-TPR and reduced catalyst characterization are reported.

DOI: 10.11949/0438-1157.20250519 · Publisher record · Evidence level: publisher abstract/metadata; full-text numeric conversion, selectivity, rate, composition and reduction protocol were not independently audited.

Vanadium conclusion: Yes—vanadium is scientifically plausible as a promoter/interface component worth testing. The direct precedent suggests a pathway-selective effect (m-cresol → toluene), not necessarily superior total HDO rate or broad guaiacol/lignin-oil performance. One direct paper cannot establish reproducibility or an activity ranking. The search also surfaced a V-containing H4PMo11VO40 + Ni/C guaiacol study, but V is embedded in a Mo heteropolyacid and the stipulated reduced Ni–V/VOx state is not established in the accessible abstract; it is adjacent evidence only, not counted.

Mechanistic context—not qualifying Ni–V papers

Practical interpretation

  1. For demonstrated breadth, NiMo currently has the larger direct evidence base in the screened set, including phenol and guaiacol and multiple supports. Do not turn the reported conversions/selectivities into a head-to-head score.
  2. For a V hypothesis, test selective oxygen removal rather than conversion alone. Include m-cresol (direct precedent) and guaiacol (broader functionality), quantify toluene/cycloalkanes/oxygenates, and report carbon balance and time-on-stream.
  3. Use matched controls: Ni/support, V/support, physical mixture, and Ni–VOx/support across a controlled Ni:V series. Match Ni loading, support batch, reduction ramp/temperature/time, passivation, particle size as far as feasible, H2 pressure, temperature, solvent and residence time.
  4. Characterize the working-state interface: H2-TPR, chemisorption, XPS/XAS where available, TEM/STEM-EDS, and post-reaction oxidation/state checks. Nominal composition alone does not prove Ni–VOx interfacial sites.
  5. Report comparable metrics: conversion; carbon-based selectivity and yield; oxygen removal/deoxygenation; rate normalized to catalyst mass and exposed Ni (if measured); deactivation and carbon balance. Separate H2 feed pressure and solvent-mediated hydrogen transfer.

This is a screening recommendation, not a published optimum or proof that V will outperform Mo.

Evidence and limitations