# Temperature‐Tuned Electrocatalytic Valorization of Levulinic Acid to γ‐Valerolactone or 4‐Hydroxyvaleric Acid over CuNi(Ru)/Graphene Nanowalls

**Authors:** Pol Vilariño, Jordi Rigual‐Miret, Ghulam Farid, Stefanos Chaitoglou, Roger Amade, Elvira Gómez, Albert Serrà

PMC · DOI: 10.1002/cssc.202502403 · Chemsuschem · 2025-11-25

## TL;DR

Researchers developed a temperature-controlled electrocatalytic system to convert levulinic acid into either γ-valerolactone or 4-hydroxyvaleric acid using CuNi(Ru)/graphene nanowalls.

## Contribution

A tunable electrocatalytic platform that switches product selectivity based on temperature using CuNiRu catalysts on graphene nanowalls.

## Key findings

- At 5°C, all catalysts showed >95% selectivity to 4-hydroxyvaleric acid.
- At 50°C, CuNiRu achieved 96.6% LA conversion and 92.4% GVL yield.
- The system showed high Faradaic efficiency (up to 89%) and energy storage efficiency (>70%).

## Abstract

Temperature‐modulated electrocatalytic hydrogenation of levulinic acid (LA) to γ‐valerolactone (GVL) or 4‐hydroxyvaleric acid (HVA) was investigated over CuNi and CuNiRu catalysts electrodeposited onto vertically aligned graphene nanowalls. Systematic potential (–1.6 to –2.0 V vs. Ag|AgCl) and temperature (5°C–50°C) studies revealed a clear product switch: at 5°C all catalysts showed > 95% selectivity to HVA, whereas at 50°C GVL dominated. Among the compositional configurations, trimetallic CuNiRu (50 mC cm−2) achieved the highest performance, affording 96.6% LA conversion, 92.4% GVL yield, and 98.5% selectivity at 50°C with minimal Ru loading. The synergy between Ru sites (promoting hydrogen activation and lactonization) and the high‐roughness nanowall scaffold suppressed H2 evolution, minimized metal leaching (<1%), and delivered stable operation under ambient pressure. The system maintained performance over multiple cycles and preserved selectivity even under concentrated LA solutions, confirming architectural robustness. Faradaic efficiencies up to 89%, low energy consumption (~0.12  kWh  mol−1), and energy storage efficiencies > 70% underscore the viability of this system for direct electricity‐to‐fuel conversion. These temperature–potential insights establish a tuneable platform where low‐temperature operation yields HVA, whereas moderate temperatures (50°C) enable near‐quantitative GVL production.

Temperature‐modulated electrocatalysis over CuNi(Ru)/graphene nanowalls (GNWs) enables tuneable biomass valorization of levulinic acid. Synergistic alloy–support interactions direct selective hydrogenation to γ‐valerolactone or 4‐hydroxyvaleric acid with high efficiency, stability, and energy performance.© 2026 WILEY‐VCH GmbH

## Linked entities

- **Chemicals:** levulinic acid (PubChem CID 11579), γ-valerolactone (PubChem CID 7921), 4-hydroxyvaleric acid (PubChem CID 114539)

## Full-text entities

- **Chemicals:** LA (MESH:C032246), 4-Hydroxyvaleric Acid (MESH:C469548), H2 (MESH:D006859), Ag (MESH:D012834), AgCl (MESH:C037548), Graphene (MESH:D006108), Ru (MESH:D012428), GVL (MESH:C037556), CuNi (-)
- **Mutations:** C-50 C

## Full text

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## Figures

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## References

76 references — full list in the complete paper: https://tomesphere.com/paper/PMC12767560/full.md

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Source: https://tomesphere.com/paper/PMC12767560