Promoting Electrocatalytic Hydrogenation of 5-Hydroxymethylfurfural over a Cooperative Ag/SnO₂ Catalyst in a Wide Potential Window

Abstract

Electrochemical reduction of biomass-derived 5hydroxymethylfurfural (HMF) to produce 2,5-dihydroxymethylfuran (DHMF) is a promising approach for biomass upgrading. The achievement of high activity and Faradaic efficiency (FE) in a wide potential window is critical for mature applications considering the significantly varied voltages supplied by different renewable energies. However, it is still challenging due to multiple reaction pathways and the competitive hydrogen evolution reaction. Herein, we synthesized a cooperative catalyst by supporting Ag nanoparticles (AgNPs) on SnO 2 nanosheet arrays, which realizes the electrochemical HMF reduction to DHMF with a high FE (>95%) in a wide potential window (from −0.62 to −1.12 V vs reversible hydrogen electrode). Electrochemical and in situ measurements reveal that the AgNPs promote water splitting to generate reactive hydrogen (H*) species, which effectively react with HMF via a Langmuir−Hinshelwood mechanism. Moreover, the AgNPs accelerate the formation of oxygen vacancies on SnO 2 under reaction conditions, which act as electrophilic sites to realize the selective adsorption and hydrogenation of the carbonyl bond (C�O) in HMF to yield DHMF. Finally, we designed a coupling system to simultaneously realize the electrochemical reduction and oxidation of HMF to produce DHMF and 2,5-furandicarboxylic acid, showing lower potential at the same current density than that of traditional cathodic HMF reduction coupling anodic oxygen evolution reaction, in an economical manner.

Amino-tethered Ni3S2/MoS2 heterojunction for coupling electrochemical 5-hydroxymethylfurfural oxidation with 4-nitrophenol hydrogenation

“…S14 and Table S1†) showed the remarkable performance of NiMoS x –NH 2 in terms of its low overpotential and high current density. 17,20,44,51 Also, Tafel plots were obtained and showed that the presence of HMF caused decreases in the slopes from 178 to 144 mV dec −1 for NiMoS x and 107 to 64 mV dec −1 for NiMoS x –NH 2 , reflecting the faster HMF oxidation rates than the OER (Fig. 2c).…”

“…Apart from the traditional hydrogen evolution reaction (HER), various other reduction reactions have been coupled with the HMFOR to afford electrocatalytic coupling systems, such as HMFOR–CO 2 RR, HMFOR–HMFHR, and HMFOR–ph-NO 2 HR, with an aim to additionally promote the efficiency, decrease the reaction potential, and simultaneously produce valuable chemicals at the cathode. 1,16–19 One typical example is the coupling of the HMFOR with the electrocatalytic hydrogenation of nitro-compounds such as 4-nitrophenol (4-NP) (Scheme 1). The product p -aminophenol (4-AP) is a vital chemical raw material and organic intermediate in fields such as pharmaceuticals, pesticides, printing, and dyeing.…”

“…A great number of electrocatalysts have been explored in the HMFOR and for coupling with other reduction reactions. 17,18 Compared with noble metal catalysts, 23 transition metal (Ni, Co, Fe, Mo, Cu)-based catalysts are low cost and earth element abundant, and their performance can be improved by doping with a heteroatom, constructing oxygen vacancies, optimizing the wettability, tuning the energy band structure and surface structure, etc. 20,24–28 Among these, Ni-based compounds, typically sulfides, nitrides, and phosphides, exhibit admirable electrocatalytic properties, with the formation of oxyhydroxides like NiOOH as the key active species.…”

Electrocatalytic hydrogenation coupling oxidation using water in a highly efficient paired cell enabled by an oxygen defect-rich layered double hydroxide

“…5–7 In particular, great attention has been paid to the preparation of high value chemical products by electrocatalytic reduction using water as the hydrogen source. 8–10 The use of electrocatalytic water splitting as a hydrogen source has been successfully extended to reduction reactions of several compounds including the reduction of nitrobenzene, 11,12 biomass such as lignin 13 and furfural, 10,14,15 benzaldehyde, 16 benzoic acid, 17 etc. However, using noble metal-based ( e.g.…”

Promoting Electrocatalytic Semihydrogenation of Alkynols to Alkenols over a Bimetallic CuAu Alloy Catalyst

“…It is documented that electrocatalytic (semi)­hydrogenation processes generally involve the adsorption of the substrate over the catalyst and simultaneous generation of adsorbed hydrogen species (H*) by water reduction, with following substrate hydrogenation using the H* species, which is known as an electrocatalytic hydrogenation process (ECH). − In our previous works, we identified that doping single-atom Ru in Cu nanowires or supported Ag nanoparticles on SnO 2 promoted H* generation, which in turn facilitated electrocatalytic hydrogenation of 5-hydroxymethylfurfural (HMF), , an important biomass platform molecule. However, excessive H* on the catalyst surface may hinder substrate adsorption and induce hydrogen evolution reaction (HER), a competitive reaction that diminishes the FE of the ECH product.…”