Selective Catalysts Research Articles

Research and selection of catalysts for the process of alkylation of oil fractions with catalytic cracking gases

The article presents the results of the study and use of modified zeolite-containing catalysts (ZSM-5) and natural alumosilicates (halloisite) in the process of alkylation of distillate fraction with catalytic cracking gases. Based on thermogravimetric analysis, it was determined that modification of halloisite with the Al+CCl4 system leads to the appearance of peaks indicating exo- and endo processes under the influence of temperature. When the oil fraction was alkylated at a temperature of 50 oC on Al+CCl4+halloisite catalyst with catalytic cracking gases containing olefins of 43.47 % the viscosity index was increased from 32 to 84. Based on NMR spectra, it was determined that alkylates differ from the original oil fraction by increased values isoparaffin index, the number of protons in aromatic structures and those furthes from the aromatic nucleus. These data confirm the improvement in the viscosity temperature characteristics of the oil fraction. Alkylation of an oil fraction with a viscosity index of 49.9 on ZSM-5 and ZSM-5-ZrO2 catalysts made it possible to obtain oils with a viscosity index of 80.7 and 137, respectively. Based on X-ray diffraction studies using rentgenographic method, it was shown that Zr is contained in the structure of ZSM-5 zeolite in the form of ZrO2. The introduction of Zr into the crystaline structure of the zeolite helps to increase the activity of the modified catalyst ZSM-5-ZrO2. Research has shown that the phase composition of samples of the modified ZSM-5-ZrO2 zeolite changes depending on the calcination temperature. An increase in temperature from 200 to 550 oC leads to the transition of the amorphous phase to the crystalline phase, and at a given calcination temperature a phase belonging to ZrO2 appears. The introduction of Zr into the catalyst composition leads to a change in the ratio of the Lewis and Brensted acid sites of the ZSM-5 catalyst. Namely, there is an increased Lewis and a decreased Brensted acid sites. Based on this it can be assumed that both Brensted and Lewis acid sites take part in the alkylation process.

Surface chlorination of IrO2(110) by HCl.

The ability to controllably chlorinate metal-oxide surfaces can provide opportunities for designing selective oxidation catalysts. In the present study, we investigated the surface chlorination of IrO2(110) by HCl using temperature programmed reaction spectroscopy (TPRS), x-ray photoelectron spectroscopy (XPS), and density functional theory (DFT) calculations. We find that exposing IrO2(110) to HCl, followed by heating to 650K in ultrahigh vacuum, produces nearly equal quantities of on-top and bridging Cl atoms on the surface, Clt and Clbr, where the Clbr atoms replace O-atoms that are removed from the surface by H2O formation. After HCl adsorption at 85K, only H2O desorbs at low Cl coverages during TPRS, but HCl begins to desorb in increasing yields as the Cl coverage is increased above about 0.5 monolayer (ML). The desorption of Cl2 was not observed under any conditions, in good agreement with the high barrier for this reaction predicted by DFT. A maximum Cl coverage of 1 ML, with nearly equal coverages of Clt and Clbr atoms, could be generated by reacting HCl with IrO2(110) in UHV. Our results suggest that a kinetic competition between recombinative HCl and H2O desorption under the conditions studied limits the saturation Cl coverage to a value less than the 2 ML maximum predicted by thermodynamics. XPS further shows that the partitioning of Cl between the Clt and Clbr states can be altered by subjecting partially chlorinated IrO2(110) to reductive or oxidative treatments, demonstrating that the Cl site population can change dynamically in response to the gas environment. Our results provide insights for understanding the chlorination of IrO2(110) by HCl and can enable future experimental studies to determine how Cl-modification alters the surface chemical reactivity of IrO2(110) and potentially enhances selectivity toward partial oxidation chemistry.

Self-powered wearable biosensor based on stencil-printed carbon nanotube electrodes for ethanol detection in sweat

Herein we introduce a novel water-based graphite ink modified with multiwalled carbon nanotubes, designed for the development of the first wearable self-powered biosensor enabling alcohol abuse detection through sweat analysis. The stencil-printed graphite (SPG) electrodes, printed onto a flexible substrate, were modified by casting multiwalled carbon nanotubes (MWCNTs), electrodepositing polymethylene blue (pMB) at the anode to serve as a catalyst for nicotinamide adenine dinucleotide (NADH) oxidation, and hemin at the cathode as a selective catalyst for H2O2 reduction. Notably, alcohol dehydrogenase (ADH) was additionally physisorbed onto the anodic electrode, and alcohol oxidase (AOx) onto the cathodic electrode. The self-powered biosensor was assembled using the ADH/pMB-MWCNTs/SPG||AOx/Hemin-MWCNTs/SPG configuration, enabling the detection of ethanol as an analytical target, both at the anodic and cathodic electrodes. Its performance was assessed by measuring polarization curves with gradually increasing ethanol concentrations ranging from 0 to 50 mM. The biosensor demonstrated a linear detection range from 0.01 to 0.3 mM, with a detection limit (LOD) of 3 ± 1 µM and a sensitivity of 64 ± 2 μW mM−1, with a correlation coefficient of 0.98 (RSD 8.1%, n = 10 electrode pairs). It exhibited robust operational stability (over 2800 s with continuous ethanol turnover) and excellent storage stability (approximately 93% of initial signal retained after 90 days). Finally, the biosensor array was integrated into a wristband and successfully evaluated for continuous alcohol abuse monitoring. This proposed system displays promising attributes for use as a flexible and wearable biosensor employing biocompatible water-based inks, offering potential applications in forensic contexts.Graphical A novel water-based graphite ink modified with multiwalled carbon nanotubes designed for the development of a wearable self-powered biosensor enabling alcohol abuse detection through sweat analysis.

Macroporous Poly(hydromethylsiloxane) Networks as Precursors to Hybrid Ceramics (Ceramers) for Deposition of Palladium Catalysts.

Poly(hydromethylsiloxane) (PHMS) was cross-linked with 1,3,5,7-tetramethyl-1,3,5,7-tetravinylcyclotetrasiloxane (D4Vi) in water-in-oil High Internal Phase Emulsions to form macroporous materials known as polyHIPEs. It was shown that in the process of pyrolysis under Ar atmosphere at 520 °C, the obtained polyHIPEs were converted to ceramers with high yields (82.8-88.0 wt.%). Structurally, the obtained ceramers were hybrid ceramics, i.e., they consisted of Si-O framework and preserved organic moieties. Macropores present in the polyHIPE precursors remained in ceramers. Ceramers contained also micro- and mesopores which resulted from the precursor's mass loss during pyrolysis. Total pore volume and BET specific surface area related to the existence of micro- and mesopores in ceramers depended on the PHMS: D4Vi ratio applied in polyHIPE synthesis. The highest total pore volume (0.143 cm3/g) and specific surface area (344 m2/g) were reached after pyrolysis of the precursor prepared with the lowest amount of D4Vi as compared to PHMS. The composite materials obtained after deposition of PdO nanoparticles onto ceramers followed by reduction of PdO by H2 were active and selective catalysts for phenylacetylene hydrogenation to styrene.

Analysis of the effects of Pr1-xCexCoO3/dolomite catalyst on energy saving and carbon reduction in biomass gasification for the production of hydrogen-rich syngas

Biomass is considered a renewable green coal, and its clean and efficient utilization is of great significance for energy conservation and carbon reduction. One of the most critical aspects of biomass gasification is the selection of an appropriate catalyst. In this study, we synthesized a catalyst with 10 % Pr1-xCexCoO3 supported on dolomite using the sol-gel method. We conducted graded internal circulation gasification experiments to produce hydrogen-rich syngas. The effects of element substitution in PrCoO3, temperature, catalyst composition, and steam injection rate on the products were investigated. The optimal gasification conditions were determined through response surface regression analysis. The data indicate that this catalyst can improve gasification efficiency, with Pr0.4Ce0.6CoO3/Dol showing the best catalytic performance. It effectively reduces the required gasification temperature and steam amount, decreases CO2 production, and increases CO and H2 yields. The catalyst accelerates the cleavage and ring-opening reactions of hydrocarbons, leading to terminal chain hydroxylation, followed by the dehydration-condensation of methyl groups into ethers. As the temperature rises, the rate of carboxyl group removal gradually exceeds the rate of carboxyl group formation via the oxidation of hydroxyl and ether chains, resulting in an initial increase and then a decrease in the number of carboxyl groups. Under optimal gasification conditions, CO2 production is reduced by one-fourth compared to using a dolomite catalyst.

Electrodes Modified with Overlayers for Enhanced CO2 Reduction Selectivity

Like many electrocatalytic reactions involving the transfer of multiple protons and electrons, the CO2 reduction reaction frequently exhibits poor selectivity among many possible products. In this presentation, I will describe our laboratory’s efforts to design electrochemical platforms that enable the control over proton transfer dynamics to electrocatalysts using molecular and polymeric overlayers with the goal of increasing product selectivity and understanding reaction mechanism. This platform is generally applicable to both molecular and metallic systems, and we demonstrate how it can be used to improve the selectivity of nonprecious metal O2 reduction and NO3 - reduction catalysts.For the CO2 reduction reaction, this strategy as applied to metal electrodes is also broadly germane and is used to modulate catalyst reactivity such that it results in the selective production of ethylene, ethanol, methanol, carbon monoxide, and methane, with examples for each with Faradaic efficiencies in excess of 70%. A common theme is that the hydrophobicity of the metal-overlayer interface frequently controls product selectivity and can steer the site of protonation events at intermediates. In this manner, for example, the selectivity of catalysts between the C2 products ethanol and ethylene can be dictated. To aid in mechanistic understanding and catalyst characterization, the majority of these studies are conducted on nominally flat metal electrodes. However, we will also describe ongoing efforts to nanostructure these CO2 reduction systems to develop selective catalysts that operate at high current densities.

(Invited) Understanding Potential Losses and pH Distribution in Electrochemical Nitrate Reduction Reaction to Ammonia

Electrochemical nitrate reduction reaction (NO3 -RR) to ammonia is a promising route to eliminate one of the major pollutants in surface and groundwater. When powered by renewable electricity, electrolysis provides a sustainable method to generate ammonia from nitrate ions, facilitating the transition from a linear to a circular economy. Optimizing the physical and chemical properties of electrolysis cells is crucial to make this process economically viable for widespread implementation. Here, we explore how the choice of current density, conductivity, pH, inter-electrode distance, membrane, catalyst, and buffer solution affect nitrate removal performance and efficiency. We develop a modeling framework to investigate the cell characteristics and fluid dynamics during electrochemical NO3-RR using both laminar and bubbly flows. To obtain more precise results, we employed the bubbly flow model (i.e., Multi-phase Fluid) to take into account how gas production near the electrode surface affects liquid velocity, pH distribution, and, ultimately, potential losses. We exploit mass transfer theory to include the current density effect on migration and diffusion. In the absence of a buffer solution, the Nernstian loss became a significant portion of the polarization loss, which increased with current density. We identified the positive effect of the membrane on energy efficiency to be more significant at smaller inter-electrode distances. This study provides insights into the origin of potential losses and pH distribution, enabling electrochemical cell optimization for renewable fuel synthesis. Next, we will discuss our recent work on designing single atom alloys (SAAs) for selective conversion of low concentration nitrate ions in natural wastewater streams from Dairy farm into ammonia. We benchmarked the catalyst's selectivity, activity, and stability following standard protocols established in the field of nitrogen fixation, including control experiments by using an electrolyte that does not contain nitrate ions and performing experiments under the same operating conditions using nitrogen isotopes (i.e., 14NO3 -, 15NO3 -).

Electrochemical Hydrogenation in Action: Redefining the Production of Commodity and Fine Chemicals

Electrocatalytic hydrogenation reactions (ECH) are increasingly recognized as promising approaches for the reductive production of both commodity and fine chemicals. Particularly when powered by renewable energies, ECH offers a sustainable alternative, avoiding the need for gaseous hydrogen, high-pressure conditions, and stoichiometric reducing agents, which often lead to excessive waste formation. Moreover, ECH processes can be conducted under mild conditions near room temperature, utilizing environmentally friendly solvents like water as a proton source. This marks them as a sustainable process for the future.1 Here, we discuss our latest advancements and challenges in advancing electrochemical hydrogenations towards significant industrial applications. We focus on critical aspects such as catalyst selection, electrode design, and the suitability of reactor concepts, illustrated through selected unsaturated organic substrates that are used industrially on a large scale. Specifically, we explore the selective semi-hydrogenation of internal and terminal alkynes as well as (di)aldehydes. Each substrate presents unique challenges and opportunities, showcasing potential pitfalls, unexpected reaction pathways, and serving as a source of inspiration for future ventures in electroorganic synthesis.1-3

(Invited) Understanding the Effect of Cell Assembly and Operation on AEM Electrolyzer Performance and Durability

Water electrolysis to produce hydrogen is gaining significant attention due to a significant decrease in the cost of renewable energy sources such as solar, wind, and tidal etc. Among the existing water electrolysis technologies, anion exchange membrane water electrolysis has recently emerged due to its potential advantages over proton exchange membrane electrolysis and traditional alkaline electrolysis. Anion exchange membrane electrolyzers (AEMELs) can allow for the use of PGM-free electrocatalysts and low-cost component materials due to its less corrosive alkaline environment while also enabling electrochemical H2 compression.An overwhelming majority of the research that is going on related to AEMELs is the synthesis of advanced functional nanomaterials – e.g. new catalysts and membranes. Though these are critically important components of the cell, their function is supported by a multitude of other factors. For example, it is well-known that water and gas transport in the electrodes is highly dictated by the porous transport layers. The electrode fabrication technique controls the electrode morphology. The synthesis method for the catalyst determines its porosity and structure. The cell gasketing controls compression. The operating current density and temperature affect stress at the material and electrode level, and dictate other properties such as exchange current, ionic conductivity, water uptake, diffusivities, etc. Many of these properties are less reported and will be the subject of this presentation.This presentation will focus on understanding how various decisions that are made regarding electrode fabrication, cell assembly and cell operation affect the operating voltage and voltage stability of AEM electrolyzers. The goal of this talk is to combine electrochemical and physical characterization data to develop a series of guiding principles for AEMEL operation that can be used across polymer chemistries and catalyst selection.

Selectivity Study of Anodic Seawater Electrolysis Catalysts Using the Rotating Ring-Disc Electrode Method

Water electrolysis generating green hydrogen will play a vital role in achieving the net-zero 2050 goal; however, freshwater electrolysis will further strain an already strained supply of clean freshwater.1 If seawater electrolysis can be scaled successfully, it would provide an important source of green hydrogen. Current research on untreated, direct seawater electrolysis is limited, and only recently have studies emerged analyzing catalyst performance at near-neutral pH.2 At industrially-relevant current densities, the formation of corrosive hypochlorite must be considered as a secondary reaction.3 Hypochlorite forms through the chloride oxidation reaction (ClOR), which competes with the oxygen evolution reaction (OER) in seawater electrolysis.2 In this work, we discuss the limitations of the current methods for determining anodic catalyst selectivity between OER and ClOR. The short lifetime of hypochlorite can cause faradaic efficiency measurement methods such as titration or oxygen gas capture to become unreliable, as these tests require that the hypochlorite remain stable. Using a rotating ring-disc electrode (RRDE), we measure the selectivity of common OER catalysts in-situ (Figure 1a). Real-time hypochlorite sensing overcomes the challenge of measuring catalyst selectivity posed by the short lifetime of hypochlorite. Remarkably, a PtRu catalyst outperformed more common OER catalysts with the best in OER selectivity and low overpotential, a novel development in the field of near-neutral water electrolysis. We also determine that elevated heat and low chlorine concentration are conducive to improved OER selectivity on an IrO2 catalyst (Figure 1b). We hope this work will set the standard in catalyst benchmarking for seawater electrolysis catalysts and could lead to the development of catalysts for efficient, scalable, and sustainable hydrogen production from seawater. H. Jin et al., Sci Adv, 9, eadi7755 (2023) https://www.science.org/doi/10.1126/sciadv.adi7755.F. Dionigi, T. Reier, Z. Pawolek, M. Gliech, and P. Strasser, ChemSusChem, 9, 962–972 (2016) https://onlinelibrary.wiley.com/doi/full/10.1002/cssc.201501581.J. Guo et al., Nature Energy 2023, 1–9 (2023) https://www.nature.com/articles/s41560-023-01195-x. Figure 1. a) LSV profiles of common OER catalysts (solid line) and the corresponding faradaic efficiency (dashed line) for the OER, measured using the ring current of the rotating ring-disc electrode. Catalysts were tested in 0.5 M NaCl and buffered with KHCO3 to pH 8.5. b) A ternary plot depicting the effect of varying Cl concentrations and temperatures on the selectivity of an IrO2 catalyst at pH 8.5. Figure 1

(Invited) Photocatalyst Sheets for Scalable Solar Fuels Production from Water and CO2

The development of sunlight-driven water splitting or CO2 reduction systems with high efficiency, scalability, and cost-competitiveness is a central issue for mass production of fuels and energy-rich chemicals.1 Z-scheme photocatalytic systems, employing the two-step photoexcitation of photocatalyst I (PC I) and photocatalyst II (PC II), have garnered significant attention. These systems can utilize narrow bandgap semiconductors capable of either water/CO2 reduction or oxidation potential, enabling the conversion of solar energy. The challenge in developing a Z-scheme system lies in ensuring efficient electron transfer between PC I and PC II.2 To address these challenges, we have developed all-solid-state devices—photocatalyst sheets—for photocatalytic water splitting.3,4 These sheets establish a direct connection between PC I and PC II particles via a conductive layer or conductive nanoparticles, effectively facilitating electron transfer between them. Consequently, these photocatalyst sheets achieve a high solar-to-H2 conversion efficiency exceeding 1%. They outperform analogous powder suspension and photoelectrochemical systems in their optimal reaction solutions due to the effective electron transfer enabled by the conductive layer or nanoparticles bridging PC I and PC II. Compared to traditional photoelectrochemical systems, the photocatalyst sheet design significantly reduces the effects of H+/OH− concentration overpotentials and the IR drop due to the proximity of PC I and PC II in the sheet. Hence, the design of these photocatalyst sheets proves highly suitable for efficient large-scale applications.Additionally, efforts to demonstrate fuel production from CO2 powered by sunlight are currently hampered by the requirements of sacrificial electron donors or external bias, and lack of efficiency, selectivity and scalability. To overcome those barriers, we integrate a selective molecular catalyst on semiconductor light absorbers to form a wireless and monolithic photocatalyst sheet.5 For instance, by incorporating a phosphonated cobalt(II) bis(terpyridine) catalyst (CotpyP) onto a modified SrTiO3:La,Rh|Au|BiVO4:Mo sheet, we have achieved a solar-to-formate conversion efficiency of 0.08%. This configuration harnesses the high selectivity of molecular catalysts for CO2 reduction and the strong water oxidation power of semiconductors, yielding a formate selectivity of 97±3% through the coupled process of CO2 reduction and water oxidation. We have also developed a bio-abiotic hybrid system by combining a photocatalyst sheet, capable of scalable photocatalytic water splitting, with nonphotosynthetic bacteria acting as biocatalysts.6 When pairing CO2-fixing acetogenic bacteria, Sporomusa ovata, with a SrTiO3:La,Rh|ITO|BiVO4:Mo sheet, a solar-to-acetate conversion efficiency of ~0.7% was achieved (as shown in the figure). This coupling exhibited an impressive selectivity for acetate production in CO2 reduction reactions, reaching ~100%.Our study offers novel and versatile strategies toward sustainable solar fuel production.References Q. Wang, C. Pornrungroj, S. Linley, E. Reisner. Nat. Energy 7 , 13–24 (2022)Y. Sasaki, H. Nemoto, K. Saito, A. Kudo. J. Phys. Chem. C 113, 17536–17542 (2009)Q. Wang, T. Hisatomi, Q. Jia, H. Tokudome, M. Zhong, C. Wang, Z. Pan, T. Takata, M. Nakabayashi, N. Shibata, Y. Li, I. D. Sharp, A. Kudo, T. Yamada, K. Domen. Nat. Mater. 15,611–615 (2016)Q. Wang, T. Hisatomi, Y. Suzuki, Z. Pan, J. Seo, M. Katayama, T. Minegishi, H. Nishiyama, T. Takata, K. Seki, A. Kudo, T. Yamada, K. Domen. J. Am. Chem. Soc. 139, 1675–1683 (2017)Q. Wang, J. Warnan, S. Rodríguez-Jiménez, J. J. Leung, S. Kalathil, V. Andrei, K. Domen, E, Reisner. Nat. Energy 5, 703–710 (2020)Q. Wang, S. Kalathil, C. Pornrungroj, D. C. Sahm, E. Reisner. Nat. Catal. 5, 633–641 (2022) Figure 1

Diagnosing Copper-Palladium Bimetallic Cathode Capability in CO2 Electrolyzers through Surface Enhanced Raman Spectroscopy

The electrochemical reduction of CO2 offers potential for utilizing CO2 as a carbon feedstock and storing intermittent renewable energy. Presently, copper stands out as the only electrocatalyst capable of reducing CO2 into multiple hydrocarbon products. However, the performance of Cu catalysts is hindered due to poor selectivity, stability and high overpotential. In addressing these bottlenecks, our research focuses on the synthesis and characterization of Pd doped Cu bimetallic catalysts, for improving the selectivity and stability of Cu catalysts during CO2 reduction. We leverage cutting-edge In-situ Shell-Isolated Nanoparticles Enhanced Raman Spectroscopy (SHINERS) to investigate structural and compositional changes on the catalyst surface during electrochemical processes within a CO2 electrolyzer. Our preliminary in-situ Raman findings indicate a strong link between the selectivity of the bimetallic electrocatalyst in CO2 electrolysis and the surface oxide phases of the catalysts. This investigation provides crucial insights for designing an efficient electrocatalyst for CO2 reduction.

Electrocatalytic Upgrading of CO2 to Light Olefins in Protonic Ceramic Electrochemical Cells

Light olefins (ethylene, propylene, butylene) are primary building blocks for chemical manufacturing of large volume products including organic chemicals, plastics, and even sustainable aviation fuels. Currently, the dominant commercial process for olefin production is steam cracking of naphtha or ethane, which is highly energy intensive and accounts for a large fraction of global CO2 emissions. To decarbonize olefin production processes, electrochemical CO2-to-olefin conversion coupled with renewable or low-emission energy sources including electricity and heat offers an attractive alternative. Previously, extensive research efforts have been devoted to low temperature electrochemical CO2 reduction in aqueous media, i.e., occurring below 100 °C. This approach, however, still faces enormous scientific and technological challenges in improving CO2 utilization, energy efficiency, and product selectivity. In this work, we have developed a new electrochemical process for direct conversion of CO2 to ethylene at intermediate temperatures (350-500°C) in an electrochemical membrane reactor. This process is based on high-performance protonic ceramic electrochemical cells (PCECs) that integrate CO2 hydrogenation reaction to produce olefins in the cathode and concurrent hydrogen generation reaction in the anode to provide hydrogen for CO2 conversion. Highly active and selective catalysts for CO2-to-olefin conversion have been identified and integrated into the PCECs. Both the catalytic and electrochemical performances of the integrated reactor system are evaluated and optimized. In contrast to the use of molecular H2 in conventional thermal catalytic pathways, the active hydrogen in PCECs could be sourced from different feedstocks including H2O, light alkanes, and ammonia, etc. This work also provides valuable insights into the selection and design of efficient catalysts for electrochemical CO2 conversion at elevated temperatures.

Rational Design and Synthesis of CO2 Reduction Reaction Catalysts of High Faradaic Efficiency Toward C2 + Chemical Conversions

Carbon dioxide emission from fossil fuel combustion poses a major threat to global environment and ecological systems.Carbon capture, sequestration and conversion technologies are widely pursued as possible solutions to mitigate negative impact by CO2. The electrochemical CO2 reduction reaction (CO2RR) to fuels and chemicals using renewable electricity offers attractive “carbon-neutral” and “carbon-negative” mitigation strategies. Various catalysts have been investigated as the electrocatalysts for CO2RR. Key challenges facing the current catalyst and electrolyzer designs include insufficient energy efficiency and low single product selectivity.CO2RR to C2+ chemicals represent a highly important area for CO2 reduction and utilization. For example, ethanol, ethylene, propanol, etc. are among the most produced chemicals by the industry and are widely used for various applications. Using CO2 as raw material for chemical production through electrocatalysis not only improves the carbon cycling, but also reduces the overall emissions from chemical production. While CO2RR via two proton-electron pairs (PEPs), such as the conversion of CO2 to CO or formate, have been proven high selective with fast kinetics, conversions to C2+ chemicals are significantly more difficult due to the rapid escalation of required PEPs to much higher numbers (for example, 12 for ethanol and 18 for propanol), in addition to C-C bond coupling. The increased PEPs substantially complicate the conversion by required multiple steps along the electrochemical coordinate, leading to a high probability of branching reactions and low single product Faradaic efficiency (FE).To address these challenges, the design criteria for CO2RR to C2+ chemicals should be based on high uniformity of active center for directing identical catalytic path and suppressing competing reactions, strong catalyst-reactant binding in capturing the transient species through multiple PEP transfers, and microenvironment with nanoconfinement for retaining reaction intermediates during extended catalytic processes.Recently, we developed a new amalgamated lithium metal (ALM) synthesis method of preparing highly selective and active CO2RR catalyst and achieved > 90% FE for conversion of CO2 to ethanol [1]. Our have since expanded the approach to other C2 + chemicals including acetate, acetone, glycerol, isopropanol, etc., all with FE at or higher than 80%. To better formulate our catalyst design strategy, we not only measured the CO2RR performance over a variety of electrocatalysts, but also investigated their activity-structure relationship through advanced material characterizations, combined with the first-principle computation. We found many interesting properties uniquely associated to CO2RR mechanism and kinetics, such as catalyst-size and electro-potential modulated single selectivity. In this presentation, we will share our recent discoveries and future perspective on the development of highly selective CO2RR catalysts for C2+ chemical conversions. Acknowledgement: This work is supported by U. S. Department of Energy, Office of Energy Efficiency and Renewable Energy - Industrial Efficiency & Decarbonization Office and by Office of Science, U.S. Department of Energy under Contract DE-AC02-06CH11357.[1] “Highly selective electrocatalytic CO2 reduction to ethanol by metallic clusters dynamically formed from atomically dispersed copper” Haiping Xu, Dominic Rebollar, Haiying He, Lina Chong, Yuzi Liu, Cong Liu, Cheng-Jun Sun, Tao Li, John V. Muntean, Randall E. Winans, Di-Jia Liu and Tao Xu, (2020) Nature Energy, 5, 623–632

Advancements in Electrocatalysts for Low-Temperature CO2 Electrolysis: Progress and Insights from the ECO2Fuel Project

The Electrochemical CO2 Reduction Reaction (CO2RR) represents a cutting-edge approach for converting CO2 into valuable chemicals and fuels, marking a significant stride in energy storage through chemical bonds. This innovative method ingeniously merges the well-established water splitting reaction with Fischer-Tropsch synthesis, traditionally dependent on high temperatures and pressures. However, uniquely, CO2RR facilitates this process under ambient conditions, combining hydrogenation with water splitting at room temperature and normal atmospheric pressure. In this context, the ECO2Fuel project, an initiative under the European Green Deal, aims to develop, implement, and validate the first-ever 1MW low-temperature direct electrochemical CO2 conversion system, poised to produce economically viable and sustainable e-fuels and chemicals.Despite its transformative potential, the ECO2Fuel project acknowledges and addresses several pivotal challenges, including enhancing catalyst performance and selectivity, electrode longevity, mass transport optimization, averting electrolyte flooding, and mitigating the hydrogen evolution reaction.This presentation will predominantly concentrate on refining the gas diffusion electrode at the cathode, for large-scale fuel and alcohol production via CO2RR. This electrode is composed of a gas diffusion layer, ensuring efficient CO2 transport; a catalyst layer where the reduction transpires; and a top adhesion layer to prevent catalyst delamination. These components collectively influence the electrode’s selectivity, durability, and stability.Our discourse will delve into the intricate aspects of the catalyst layer and porous transport layer design, along with electrode manufacturing techniques, demonstrating their critical roles in achieving high faradaic efficiencies for carbonaceous fuel production. Furthermore, we will explore the nuanced operational modalities of the CO2 electrolyzer cell, focusing on strategies to curtail the parasitic side reaction of hydrogen evolution, thereby enhancing the system's overall efficiency and productivity.This project has received funding from the European Union’s Horizon 2020 research and Innovation program under grant agreement no. 202037389.

Electrochemical Conversion of Low-Cost Glycerol to Valuable Products

Over the last years, biodiesel production, a renewable fuel derived from biomass, has significantly increased, reaching an output of 40 million tons annually. This surge in production has resulted in excessive glycerol production, as a byproduct, accounting for 10 wt.% of biodiesel production. By 2025, it is predicted that glycerol production will amount to 6.3 million tons.1 However, the low demand for glycerol not only causes high disposal costs for this waste byproduct but also poses a threat to the ecosystem. Consequently, the valorization of glycerol is crucial for enhancing the biodiesel industry's economic viability and environmental sustainability.Among all the techniques for the valorization of glycerol, such as catalytic oxidation, dehydration, and hydrogenolysis, the electrochemical oxidation of glycerol stands out for its cost-effectiveness, simplicity, and eco-friendliness. The glycerol electrooxidation reaction (GOR) can yield a wide range of valuable chemicals, such as C3 products (glyceraldehyde, lactic acid, glyceric acid, tartronic acid), C2 products (glycolic acid, oxalic acid, acetic acid), and C1 products (formic acid). Among all the products, C3 products have notably higher economic value compared to others. In particular, glyceric acid stood out by having a price of over 200 folds of glycerol and having the highest worldwide demand among all the GOR products.2 However, a significant technical challenge lies in developing a highly selective catalyst for C3 products showing high activity, and stability. Thus far, most of the catalyst developed for GOR includes noble metals or their alloys, which limits their usage in realistic systems due to their high cost and scarcity.3 Therefore, developing a cost-effective catalyst with high selectivity, activity, and stability is necessary to make the valorization of glycerol economically viable.In this work, we demonstrate a bimetallic catalyst that, despite its low noble metal content, achieves high selectivity towards glyceric acid, along with notable catalytic activity and stability. Our analysis focuses on the impact of noble metal amount on activity and stability, and parametric analysis to improve the selectivity of C3 products. Furthermore, we outline the reasons for the discrepancies in the quantification of GOR products, especially in applying H-NMR analysis, and discuss the methods to improve the precision in GOR product analysis.

Enhancing Electrocatalytic Semihydrogenation of Alkynes via Weakening Alkene Adsorption over Electron-Depleted Cu Nanowires.

Electrochemical semihydrogenation (ESH) of alkynes to alkenes is an appealing technique for producing pharmaceutical precursors and polymer monomers, while also preventing catalyst poisoning by alkyne impurities. Cu is recognized as a cost-effective and highly selective catalyst for ESH, whereas its activity is somewhat limited. Here, from a mechanistic standpoint, we hypothesize that electron-deficient Cu can enhance ESH activity by promoting the rate-determining step of alkene desorption. We test this hypothesis by utilizing Cu-Ag hybrids as electrocatalysts, developed through a welding process of Ag nanoparticles with Cu nanowires. Our findings reveal that these rationally engineered Cu-Ag hybrids exhibit a notable enhancement (2-4 times greater) in alkyne conversion rates compared to isolated Ag NPs or Cu NWs, while maintaining over 99% selectivity for alkene products. Through a combination of operando and computational studies, we verify that the electron-depleted Cu sites, resulting from electron transfer between Ag nanoparticles and Cu nanowires, effectively weaken the adsorption of alkenes, thereby substantially boosting ESH activity. This work not only provides mechanistic insights into ESH but also stimulates compelling strategies involving hybridizing distinct metals to optimize ESH activity.

Electrochemical CO2Reduction Reaction: Comprehensive Strategic Approaches to Catalyst Design for Selective Liquid Products Formation.

The escalating concern regarding the release of CO2 into the atmosphere poses a significant threat to the contemporary efforts in mitigating climate change. Amidst a multitude of strategies for curtailing CO2 emissions, the electrochemical CO2 reduction presents a promising avenue for transforming CO2 molecules into a diverse array of valuable gaseous and liquid products, such as CO, CH3OH, CH4, HCO2H, C2H4, C2H5OH, CH3CO2H, 1-C3H7OH and others. The mechanistic investigations of gaseous products (e.g. CO, CH4, C2H4, C2H6 and others) broadly covered in the literature. There is a noticeable gap in the literature when it comes to a comprehensive summary exclusively dedicated to coherent roadmap for the designing principles for a selective catalyst all possible liquid products (such as CH3OH, C2H5OH, 1-C3H7OH, 2-C3H7OH, 1-C4H9OH, as well as other C3-C4 products like methylglyoxal and 2,3-furandiol, in addition to HCO2H, AcOH, oxalic acid and others), selectively converted by CO2 reduction. This entails a meticulous analysis to justify these approaches and a thorough exploration of the correlation between materials and their electrocatalytic properties. Furthermore, these insightful discussions illuminate the future prospects for practical applications, a facet not exhaustively examined in prior reviews.

VO Supported on Functionalized CNTs for Oxidative Conversion of Furfural to Maleic Anhydride

Commercial non-functionalized (CNTs) and functionalized carbon nanotubes (CNT-COOH and CNT-NH2) were used as supports to synthesize vanadium-supported catalysts to be used in the gas phase partial oxidation of furfural towards maleic anhydride (MA). The CNTs and the VO2-V2O5/CNTs, so-called VO/CNT catalysts, were characterized by AAS, TGA, XRD, N2 adsorption isotherms at −196 °C, Raman, NH3-TPD and XPS. The surface area values, TGA and XRD results indicate that the larger thermal stability and larger dispersion of vanadium species is reached for the VO/CNT-NH2 catalyst. XPS indicates presence of surface VO2 and V2O5 species for the non-functionalized (CNT) and functionalized (CNT-COOH and CNT-NH2) catalysts, with a large interaction of the functional group with the surface vanadium species only for the VO/CNT-NH2 catalyst. The catalytic activity, evaluated in the range 305 °C to 350 °C, indicates that CO, CO2 and MA yield (%) and MA productivity are associated to the redox properties of the vanadium species, the oxygen exchange ability of the support and the vanadium–support interaction. For the reaction temperatures between 320 °C and 335 °C, the maximum MA yield (%) is found in the functionalized VO/CNT-COOH and VO/CNT-NH2 catalysts. This behavior is attributed to a decreased oxidation capability of the CNT with the functionalization. In addition, VO/CNT-NH2 is the more active and selective catalyst for MA productivity at 305 °C and 320 °C, which is related to the greater interaction of the surface vanadium species with the -NH2 group, which enhances the redox properties and stabilization of the VO2 and V2O5 surface active sites. Recycling at 350 °C resulted in 100% furfural conversion for all catalysts and a similar MA yield (%) compared to the fresh catalyst, indicating no loss of surface active sites.

Nitrogen-Tungsten Oxide Nanostructures on Nickel Foam as High Efficient Electrocatalysts for Benzyl Alcohol Oxidation.

Electrocatalytic alcohol oxidation (EAO) is an attractive alternative to the sluggish oxygen evolution reaction in electrochemical hydrogen evolution cells. However, the development of high-performance bifunctional electrocatalysts is a major challenge. Herein, we developed a nitrogen-doped bimetallic oxide electrocatalyst (WO-N/NF) by a one-step hydrothermal method for the selective electrooxidation of benzyl alcohol to benzoic acid in alkaline electrolytes. The WO-N/NF electrode features block-shaped particles on a rough, inhomogeneous surface with cracks and lumpy nodules, increasing active sites and enhancing electrolyte diffusion. The electrode demonstrates exceptional activity, stability, and selectivity, achieving efficient benzoic acid production while reducing the electrolysis voltage. A low onset potential of 1.38 V (vs. RHE) is achieved to reach a current density of 100 mA cm-2 in 1.0 M KOH electrolyte with only 0.2 mmol of metal precursors, which is 396 mV lower than that of water oxidation. The analysis reveals a yield, conversion, and selectivity of 98.41%, 99.66%, and 99.74%, respectively, with a Faradaic efficiency of 98.77%. This work provides insight into the rational design of a highly active and selective catalyst for electrocatalytic alcohol oxidation.