Glycol Oxidation Reaction Research Articles

Advanced low-dimensional PdAg networked nanochains for the superior alcohol electrocatalysis

Advanced 1D materials have become the focus due to the enhanced structure durability than 0D nanoparticles (NPs). Unfortunately, the unique electrocatalysts with 0D-1D composite structure are rarely reported. Herein, the low-dimensional PdAg networked nanochains (NNCs) with diverse element composition assembled from a sequence of NPs were designed as efficient 0D-1D electrocatalysts toward the ethylene glycol oxidation reaction (EGOR) and ethanol oxidation reaction (EOR). The low-dimensional PdAg NNCs not only possess stronger structure stability than 0D NPs, but also endow catalysts with more abundant active sites than traditional 1D nanochains. Attributed to the synergistic electronic effect, abundant active sites and surface defects, the composition-optimized PdAg-2 NNCs behaved the optimal electrocatalytic activities, greatly surpassing most of reported studies. Benefiting from 0D-1D composite structure and stable networked nanochain feature, the PdAg-2 NNCs still remained higher current density after the 3600 s chronoamperometry (CA) experiment and without obvious decline through three consecutive CA tests compared to commercial Pd/C, revealing the remarkable stability. Meanwhile, the PdAg-2 NNCs exhibited the prominent anti-CO poisoning ability and the lowest onset oxidation potential, manifesting the enhanced reaction kinetics. This work fabricated a novel electrocatalyst with low-dimension composite structure, producing new guidelines for the synthesis of high-efficiency electrocatalysts.

Mesoporous Mo-doped PtBi intermetallic metallene superstructures to enable the complete electrooxidation of ethylene glycol.

Metallenes, intermetallic compounds, and porous nanocrystals are the three types of most promising advanced nanomaterials for practical fuel cell devices, but how to integrate the three structural features into a single nanocrystal remains a huge challenge. Herein, we report an efficient one-step method to construct freestanding mesoporous Mo-doped PtBi intermetallic metallene superstructures (denoted M-PtBiMo IMSs) as highly active and stable ethylene glycol oxidation reaction (EGOR) catalysts. The materials retained their catalytic performance, even in complex direct ethylene glycol fuel cells (DEGFCs). The M-PtBiMo IMSs showed EGOR mass and specific activities of 24.0 A mgPt-1 and 61.1 mA cm-2, respectively, which were both dramatically higher than those of benchmark Pt black and Pt/C. In situ infrared spectra showed that ethylene glycol underwent complete oxidation via a 10-electron CO-free pathway over the M-PtBiMo IMSs. Impressively, M-PtBiMo IMSs demonstrated a much higher power density (173.6 mW cm-2) and stability than Pt/C in DEGFCs. Density functional theory calculations revealed that oxophilic Mo species promoted the EGOR kinetics. This work provides new possibilities for designing advanced Pt-based nanomaterials to improve DEGFC performance.

Amine oxide surfactant-mediated synthesis of plate-based gold nanocrystals with tunable surface wrinkles and their applications in the ethylene glycol oxidation reaction

Gold nanoplates with tunable surface wrinkles are prepared using an amine oxide surfactant, showing improved EGOR activity due to enriched uncoordinated active sites.

Electrocatalytic upgrading of polyethylene terephthalate plastic to formic acid at an industrial-scale current density via Ni-MOF@MnCo-OH catalyst

Electrocatalytic polyethylene terephthalate (PET) waste upgrading is crucial for developing a circular plastics economy and solving the energy crisis, but achieving efficient PET upgrading at an industrial-scale current density remains a formidable challenge. In our work, Ni-MOF@MnCo-OH catalyst was prepared by designing hierarchical heterostructure and incorporating the concept of multi-metal sites, wherein the Ni-MOF can be derived from PET plastic. Benefiting from the advantages of material design, the catalyst demonstrates excellent adsorption capabilities for both OHad and ethylene glycol (EG), while also enhancing the electron transfer capability of Ni-MOF. We achieve a high Faradaic efficiency (∼80 %) during PET plastic upgrading at industrial-scale current density (300 mA·cm−2 at 1.43 V vs. RHE) with Ni-MOF@MnCo-OH. Moreover, through theoretical calculations and in situ Fourier transform infrared (FTIR) spectroscopy, we have further elucidated the mechanism of ethylene glycol oxidation reaction (EGOR). Notably, glycolic acid has been identified as a vital intermediate during the electrical oxidation of EG. This work provides a viable and eco-friendly approach to enhance the value of PET waste through sustainable means.

Palladium chalcogenide nanosheets with p-d orbital hybridization for enhanced alcohol electro-oxidation performance

Ethanol oxidation reaction (EOR) is an important energy conversion process. Herein, we have proposed palladium chalcogenide nanosheets to improve C-C bond cleavage ability for EOR. The mass activity of the Te-Pd nanosheets (NSs)/C, which is higher than Se-Pd NSs/C and S-Pd NSs/C (6.9 A mg−1 and 5.3 A mg−1), has achieved 10.0 A mg−1, 12.5-fold higher than commercial Pd/C (0.8 A mg−1) and 8.3 times higher than Pd NSs/C (1.2 A mg−1). The Faradaic efficiency of C1 pathway for EOR on the Te-Pd NSs/C can improve to 56.6% compared with Pd NSs/C (25.7%) at 0.8 VRHE. Density functional theory calculations reveal that the orbital hybridization between Pd and Te weakens the adsorption energy of intermediates and reduces the energy barrier of the rate-determining steps in the C1 pathway. Besides, these palladium chalcogenide NSs can also serve as efficient electrocatalysts for ethylene glycol oxidation reaction and methanol oxidation reaction.

Alkali Etching of Porous PdCoZn Nanosheets for Boosting C-C Bond Cleavage of Ethylene Glycol Oxidation.

Pd-based electrocatalysts are the most effective catalysts for ethylene glycol oxidation reaction (EGOR), while the disadvantages of poor stability, low resistance to neutrophilic, and low catalytic activity seriously hamper the development of direct ethylene glycol fuel cells (DEGFCs). In this work, defect-riched PdCoZn nanosheets (D-PdCoZn NSs) with ultrathin 2D NSs and porous structures are fabricated through the solvothermal and alkali etching processes. Benefiting from the presence of defects and ultrathin 2D structures, D-PdCoZn NSs demonstrate excellent electrocatalytic activity and good durability against EGOR in alkaline media. The mass activity and specific activity of D-PdCoZn NSs for EGOR are 9.5Amg-1 and 15.7mAcm-2 , respectively, which are higher than that of PdCoZn NSs, PdCo NSs, and Pd black. The D-PdCoZn NSs still maintain satisfactory mass activity after long-term durability tests. Meanwhile, in situ IR spectroscopy demonstrates that the presence of defects attenuated the adsorption of intermediates, which improves the selectivity of the C1 pathway with excellent anti-CO poisoning performance. This work not only provides an effective synthetic strategy for the preparation of Pd-based nanomaterials with defective structures but also indicates significant guidance for optimum C1 pathway selectivity of ethylene glycol and other challenging chemical transformations.

In-situ synthesis of carbon-supported ultrafine trimetallic PdSnAg nanoparticles for highly efficient alcohols electrocatalysis

Designing functional and durable electrocatalysts for the oxidation of alcohols plays a significant role for the development of direct alcohol fuel cells (DAFCs). Herein, carbon-supported ultrafine PdSnAg nanoparticles with an average size of 3.27 nm (denoted as PdSnAg/C NPs) have been synthesized for alcohols electrocatalysis. The smaller particle size means a higher proportion of surface exposed atoms for catalyzing the reaction followed by high catalytic performance. The multimetallic nanoalloys have potential electronic structure adjustment and synergistic effect between different components. The incorporation of oxophilic metals Sn and Ag facilitates the removal of intermediates produced during the oxidation of alcohols. The PdSnAg/C NPs exhibit a remarkable electrocatalytic performance for ethylene glycol oxidation reaction (EGOR) with the mass activity of 12.3 A mgPd-1, which is 15.6, 2.50 and 2.60 times higher than those of commercial Pd/C (0.790 A mgPd-1), PdSn/C NPs (4.85 A mgPd-1) and PdAg/C NPs (4.69 A mgPd-1), respectively. Meanwhile, PdSnAg/C NPs show superior mass activities of 10.6 A mgPd-1 and 6.65 A mgPd-1 for ethanol oxidation reaction (EOR) and glycerol oxidation reaction (GOR), which are 14.3 and 8.30 times superior than the commercial Pd/C, respectively. The exceptional mass activity promises the PdSnAg/C NPs to be the potential Pd-based catalysts for alcohols electrocatalysis.

Ultra-efficient electrooxidation of ethylene glycol enable by Pd-loaded Fe-doped Nb2O5 with abundant oxygen vacancies

Niobium pentoxide (Nb2O5) has emerged as a highly promising electrocatalyst for ethylene glycol oxidation reaction (EGOR) due to its eco-friendly nature and its ability to maintain structural stability in alkaline environments. However, its inherent electronic structure has posed a significant barrier to further enhancing of EGOR activity. In this study, we successfully synthesized Pd-based electrocatalysts by incorporating Fe-doped Nb2O5 with abundant oxygen vacancies (Pd/FNO-2.5), which effectively promoted ethylene glycol oxidation. The results showed that the introduction of Fe doping not only altered the electronic structure of Nb2O5, leading to the generation of oxygen vacancies, but also decreased the d-band center of Pd, thereby reducing thermodynamic energy barrier of the rate-determining step by approximately 0.58 eV. Impressively, the Pd/FNO-2.5 catalyst demonstrated remarkable electrocatalytic performance exhibiting a relatively low initial potential (−0.11 V) and high mass activity (0.380 A mg−1Pd). Furthermore, even after undergoing 100 consecutive recycling experiments, the Pd/FNO-2.5 catalyst still retained 81.10 % of its current density. This study demonstrates that doping-induced oxygen vacancy engineering is a promising approach for developing efficient EGOR electrocatalysts for direct ethylene glycol fuel cells, which is associating with the efficient and sustainable development of fuel cell and the carbon neutrality efforts.

Abundant Exterior/Interior Active Sites Enable Three-Dimensional PdPtBiTe Dumbbells C-C Cleavage Electrocatalysts for Actual Alcohol Fuel Cells.

Developing high-activity electrocatalysts is of great significance for the commercialization of direct alcohol fuel cells (DAFCs), but it still faces challenges. Herein, three-dimensional (3D) porous PdPtBiTe dumbbells (DBs) were successfully fabricated via the visible photoassisted method. The alloying effect, defect-rich surface/interface and nanoscale cavity, and open pores make the 3D PdPtBiTe DBs a comprehensive and remarkable electrocatalyst for the C1-C3 alcohol (ethanol, ethylene glycol, glycerol, and methanol) oxidation reaction (EOR, EGOR, GOR, and MOR, respectively) in an alkaline electrolyte, and the results of in situ Fourier transform infrared spectra revealed a superior C-C bond cleavage ability. The 3D PdPtBiTe DBs exhibit ultrahigh EOR, EGOR, GOR, and MOR mass activities of 25.4, 23.2, 16.8, and 18.3 A mgPd + Pt-1, respectively, considerably surpassing those of the commercial Pt/C and Pd/C. Moreover, the mass peak power densities of 3D PdPtBiTe DBs in actual ethanol, ethylene glycol, glycerol, or methanol fuel cells increase to 409.5, 501.5, 558.0, or 601.3 mW mgPd + Pt-1 in O2, respectively. This study provides a new class of multimetallic nanomaterials as state-of-the-art multifunctional anode electrocatalysts for actual DAFCs.

Electron Regulation of Heterostructured Pt/Rh Metallene Boosts Ethylene Glycol Electrooxidation and Hydrogen Evolution.

The research on high-efficiency two-dimensional (2D) catalytic materials for the small-molecule oxidation-assisted hydrogen evolution reaction (HER) is prospective for efficient hydrogen production. Herein, we report heterostructured Pt/Rh metallene with Pt nanoparticles (NPs) uniformly anchored on Rh metallene for the HER and ethylene glycol oxidation reaction (EGOR). The ultrathin sheet structure of the Pt/Rh metallene offers high surface areas and sufficient active sites. More importantly, the Pt/Rh heterostructure can optimize catalytic active centers and adjust electronic structure. Thus, Pt/Rh metallene exhibits superior electrocatalytic HER activity with a low overpotential of 28 mV in 1 M KOH at 10 mA cm-2 and EGOR activity with a specific activity of 8.39 mA cm-2 in 1 M KOH with 3 M EG, along with outstanding CO tolerance. In a two-electrode system, Pt/Rh metallene requires a low potential of 0.51 V for stable and efficient hydrogen production at 10 mA cm-2 in 1 M KOH + 3 M EG, with the simultaneous production of high-value-added products. The job proposes an attractive strategy for the synthesis of 0D/2D metallene toward simultaneous energy-saving hydrogen production and chemical update.

The electrocatalytic activity and selectivity of ethylene glycol oxidation into value-added chemicals at iron-group electrodes in alkaline media

Selective electrocatalytic conversion via ethylene glycol oxidation reaction (EGOR) at abundant Iron-group catalysts could be a promising and sustainable approach to produce value-added C1 and C2 chemicals. However, the corresponding intrinsic electrocatalytic activity and selectivity of EGOR on Iron-group electrodes are still ambiguous, which is urgent to be revealed. The linear scanning voltammetry (LSV) results show that Co and Ni rather than Fe exhibit considerably high activity, and the CoIV and NiIII sites formed at high potential might be crucial for the fast EGOR revealed by LSV and operando electrochemical impedance spectroscopy (EIS). Then, the in-situ electrochemical infrared absorption spectroscopy (IRAS) and high-performance liquid chromatography (HPLC) are used to obtain a general understanding of reaction pathways and product distributions in alkaline media. Specifically, a parallel C1 pathway (formate) without CO2 generation and C2 pathway (glycollate, oxalate) is confirmed on Co and Ni surfaces. The C1 pathway is dominated on the Ni surface with a ∼60% selectivity of formate, while the C2 pathway is favorable on the Co surface with a ∼43% selectivity of glycollate at 1.60 V vs. RHE. In addition, the Ni electrode showed a higher yield rate of carboxylate products. This work may offer theoretical guidance for the design of noble-metal-free electrocatalysts towards efficient selective electrooxidation of EG to value-added chemicals.

One-pot synthesis of 3D surface-wrinkled PdAu nanospheres for robust alcohols electrocatalysis

Three dimensional (3D) noble-metal nanomaterials with special surface structures have been regarded as high-performance catalysts for alcohol oxidation on account of their superior thermal stability, electrical conductivity and large specific surface area. Although extensive efforts have been devoted to the preparation of 3D Pd-based catalysts with superior activity and stability, designing a simple, effective and eco-friendly method remains a challenge. Herein, we developed a facile one-step coreduction strategy to synthesize a series of 3D surface-wrinkled PdAu nanospheres (NSs) with tunable Pd/Au atomic ratios and found a universal method to prepare surface-wrinkled PdM (M = Au, Pt, Cu and Pb) NSs. Benefiting from the function of the surfactant cetyltrimethylammonium chloride (CTAC), the synthesized PdAu NSs with different composition possess abundant surface wrinkles, which is beneficial for exposing more electroactive centers. Attributed to the unique geometric morphology and optimized atomic ratio, the PdAu-2 NSs exhibited an optimal mass activity (MA) of 8103 mA mg−1 and 5113 mA mg−1 for the ethylene glycol oxidation reaction (EGOR) and ethanol oxidation reaction (EOR), which was 6.1 and 4.1 times that of commercial Pd/C, respectively. Moreover, the PdAu-2 NSs exhibited superb stability after long-term current–time (i-t) and cyclic voltammetry (CV) tests of the EGOR and EOR. This work not only provides new avenues to engineer PdAu NSs with enhanced electrocatalytic performance but also offers guidance for extending to more 3D PdM (M = other metals) NSs with novel morphology applied to fuel cell fields.

Improved electrocatalytic performance of Ni nano pebbles decorated 2D Fe based MXene nanosheets for direct alcohol (methanol, ethanol and ethylene glycol) fuel cell application

In this work, we report the solid-state reaction-assisted synthesis of the iron-based MAX phase compound (Fe3AlC2 MAX; where M- metal, A- aluminum, and X- carbide), which is solvothermal etched and exfoliated to yield 2D iron (Fe)-MXene. The nanosheet-like morphology of the Fe-MXene is confirmed via TEM and SEM analysis. The 2D Fe-MXene nanosheets are further decorated with nickel (Ni) nano pebbles through the simple electrodeposition technique on a screen-printed carbon electrode (Ni@FC/SPCE). The electrode displays a peak mass activity of 525.5, 742.8, and 910.2 mA/mg for methanol oxidation reaction (MOR), ethanol oxidation reaction (EOR), and ethylene–glycol oxidation reaction (EgOR), respectively. The Ni nano pebbles have excellent electrocatalytic activity owing to their multiple oxidation states (Ni2+/Ni3+) and catalytic active sites which enhance the alcohol oxidation reaction while the metallic sites of the Fe3C2 nanosheets contribute to high electrical conductivity and stability of the electrode. The as-fabricated Ni@FC/SPCE electrode exhibits high stability with outstanding capacity retention of ∼ 88%, ∼95%, and ∼ 75% for MOR, EOR, and EgOR after 10000 s of chronoamperometry analysis. This performance of the Ni@FC/SPCE as a non-noble, cost-effective, and stable nano-catalyst with excellent anti-carbon monoxide (anti-CO) poisoning properties proves it an ideal platform for DAFC applications.

Nanoflower core-shell Cu@Pd catalysts for glycol oxidation reaction with an enhanced performance

Direct alcohol fuel cells' performance is significantly affected by the phase and composition of the catalyst, thereby the development of high-performance alcohol oxidation catalysts is essential. In this study, PVA preparation was used for the first time to create PdCu core-shell nanoflowers with a high electrochemically active surface area and a potent synergistic effect. Notably, the presence of PVA causes Pd and Cu nanoparticles with different reduction rates to form a core-shell structure, and the Pd nanoparticles continue to migrate regularly under the action of PVA, forming a flower-like morphology with a high degree of branching. Cu@Pd22.3 catalyst exhibited 13 times higher catalytic performance (4353.04 mA mgPd−1) than Pd/C (334.09 mA mgPd−1) in ethylene glycol oxidation reaction. The Cu@Pd22.3 catalyst also exhibits higher stability than commercial Pd/C in stability tests lasting up to 20,000 s. This core-shell combination and highly branched structural design result in more active sites for fast ion adsorption/desorption,offering an original method to improving the activity and endurance of polyol oxidation.

Promotion effects of Pr-doped CeO2·H2O to Pt catalysts toward alcohol electrooxidation reaction

Considering that the co-catalyst which are rich in oxygen vacancy and hydroxyl functional groups have an obvious role in improving the activity and durability of Pt-based electrocatalyst, a novel Pr-doped CeO2·H2O cocatalyst (PrxCey(OH)a) has been prepared through a facile one-step hydrothermal method. The substitution of Pr3+ cation for host Ce4+ cation produces oxygen vacancies due to charge compensation effects. Pt/C-Pr1Ce6(OH)a exhibits an outstanding electrochemical oxidation performance with high peak current density of 2587 mA mg−1, 4116 mA mg−1, 2158 mA mg−1 in methanol, ethylene glycol, and glycerol oxidation reaction, respectively. PrxCey(OH)a provides significant co-catalysis effects by comparing with the alcohol electrooxidation performance of Pt/C, which shows a feasible strategy for the rational design of direct alcohol fuel cells catalysts.

Cu2+-regulated one-pot wet-chemical synthesis of uniform PdCu nanostars for electrocatalytic oxidation of ethylene glycol and glycerol

The fabrication of effective and stable electrocatalysts is crucial for practical applications of direct alcohol fuel cells (DAFCs). In this study, bimetallic PdCu nanostars (PdCu NSs) were fabricated by a Cu2+-modulated one-pot wet-chemical method, where cetyltrimethyl ammonium bromide (CTAB) worked as a structure-regulating reagent. The morphology, compositions, crystal structures and formation mechanism of the as-prepared PdCu NSs were investigated by a series of techniques. The unique architectures created abundant active sites, which resulted in a large electrochemical active surface area (9.5 m2 g−1). The PdCu NSs showed negative shifts in the onset potentials and large forward peak current densities by contrast with those of commercial Pd black for the catalytic ethylene glycol oxidation reaction (EGOR) and glycerol oxidation reaction (GOR). It revealed that the PdCu NSs outperformed Pd black in the similar surroundings. This work provides a constructive strategy for fabrication of high-efficiency electrocatalysts for alcohol fuel cells.

Activable Ru-PdRu nanosheets with heterogeneous interface for High-efficiency alcohol oxidation reaction

Fabricating 2D nanomaterials with heterogeneous structure is a feasible way to improve catalytic performance owing to its large surface area and tunable electron structure. However, such a category has not been widely reported in the field of alcohol oxidation reaction (AOR). In this work, we reported a new type of heterostructure nanosheet with Ru nanoparticles decorated around the edge of PdRu nanosheets (Ru-PdRu HNSs). Particularly, strong electronic interaction and sufficient active sites attributed to the construction of heterogeneous interface, is the key to the superior electrocatalytic behavior of Ru-PdRu HNSs towards methanol oxidation reaction (MOR), ethylene glycol oxidation reaction (EGOR), and glycerol oxidation reaction (GOR). Remarkably, owing to the enhanced electron transfer brought by the introduction of the Ru-PdRu heterogeneous interface, these novel nanosheets are highly durable. Apart from being able to maintain the highest current density after 4000 s chronoamperometry test, Ru-PdRu HNSs can be reactivated with negligible activity loss in MOR and GOR test after four consecutive i-t experiments. Impressively, in the EGOR test, after reactivation, the current density is step-wisely increased, making it one of the best AOR electrocatalysts.

Atom-stepped surface-regulated Pd nanowires for boosting alcohol oxidation activity

A highly active surface can endow the electrocatalysts with extraordinary catalytic performances. However, it remains challenging to tailor the atomic packing characteristics and thus the physical and chemical characteristics of the electrocatalysts. Herein, penta-twinned Pd nanowires (NWs) with abundant high-energy atomic steps (i.e., stepped Pd) are synthesized by seeded synthesis on Pd NWs enclosed by (100) facets. Benefiting from the catalytically active atomic steps, such as [n(100) × m(111)] on the surface, the resultant stepped Pd NWs can work as an effective electrocatalyst for the ethanol oxidation reaction (EOR) and ethylene glycol oxidation reaction (EGOR), which are essential anode reactions in direct alcohol fuel cells (DAFCs). Compared with commercial Pd/C, the Pd nanowires bound by (100) facets and atomic steps both display enhanced catalytic activity and stability towards the EOR and EGOR. Importantly, the mass activities of the stepped Pd NWs toward the EOR and EGOR are 6.38 and 7.98 A mgPd−1, which are 3.1 and 2.6 times those of Pd NWs enclosed by (100) facets, respectively. Besides, our synthetic strategy also enables the formation of bimetallic Pd-Cu nanowires with abundant atomic steps. This work not only demonstrates a simple yet effective strategy to obtain mono- or bi-metallic nanowires with abundant atomic steps, but also highlights the significant role of atomic steps for boosting the activity of electrocatalysts.

Ultra-thin CoNi0.2P nanosheets for plastics and biomass participated hybrid water electrolysis

Designing cost-efficient and active electrocatalysts are very crucial for their practical implementation in electrochemical energy conversion systems. Herein, a handy template-post phosphatization approach is adopted to achieve ultra-thin CoNi0.2P nanosheets attached to nickel foam (termed as CoNi0.2P-uNS/NF) nanohybrids. Profiting from ultra-thin construction and the optimization of electronic structure, CoNi0.2P-uNS/NF exhibits high electroactivity for hydrogen evolution reaction (HER), which only needs an overpotential of 43 mV to obtain the current density of 10 mA cm−2. Additionally, CoNi0.2P-uNS/NF also reveals prominent electroactivity for ethylene glycol oxidation reaction (EGOR) in an alkaline environment due to the surface electrochemical reconstruction. Additionally, CoNi0.2P-uNS/NF also reveals similar high electroactivity for glycerol and furfural derivatives oxidation reaction, revealing its potential as a composition-controlled platform catalyst. For practical application, CoNi0.2P-uNS/NF||CoNi0.2P-uNS/NF electrolyzer is assembled to directly electrolyze the hydrolysate of polyethylene terephthalate (i.e., the mixture of terephthalate and ethylene glycol) for the co-generation of formate and hydrogen, accompanying with lower integral electrolytic voltage (1.24 V) than traditional water splitting (1.53 V) at current density 50 mA cm−2. This work expands the territory for energy-saving co-generation of hydrogen and value-added chemical products.

Selective Ethylene Glycol Oxidation to Formate on Nickel Selenide with Simultaneous Evolution of Hydrogen.

There is an urgent need for cost-effective strategies to produce hydrogen from renewable net-zero carbon sources using renewable energies. In this context, the electrochemical hydrogen evolution reaction can be boosted by replacing the oxygen evolution reaction with the oxidation of small organic molecules, such as ethylene glycol (EG). EG is a particularly interesting organic liquid with two hydroxyl groups that can be transformed into a variety of C1 and C2 chemicals, depending on the catalyst and reaction conditions. Here, a catalyst is demonstrated for the selective EG oxidation reaction (EGOR) to formate on nickel selenide. The catalyst nanoparticle (NP) morphology and crystallographic phase are tuned to maximize its performance. The optimized NiS electrocatalyst requires just 1.395V to drive a current density of 50 mAcm-2 in 1m potassium hydroxide (KOH) and 1m EG. A combination of in situ electrochemical infrared absorption spectroscopy (IRAS) to monitor the electrocatalytic process and ex situ analysis of the electrolyte composition shows the main EGOR product is formate, with a Faradaic efficiency above 80%. Additionally, C2 chemicals such as glycolate and oxalate are detected and quantified as minor products. Density functional theory (DFT) calculations of the reaction process show the glycol-to-oxalate pathway to be favored via the glycolate formation, where the CC bond is broken and further electro-oxidized to formate.