Electrochemical reduction of carbon dioxide to produce formic acid coupled with oxidative conversion of biomass

Electrochemical reduction of CO_(2)(CO_(2)RR)has become a research hot spot in recent years in the context of carbon neutrality.HCOOH is one of the most promising products obtained by electrochemical reduction of CO_(2) due to its high energy value as estimated by market price per energy unit and wide application in chemical industry.Biomass is the most abundant renewable resource in the natural world.Coupling biomass oxidative conversion with CO_(2)RR driven by renewable electricity would well achieve carbon negativity.In this work,we comprehensively reviewed the current research progress on CO_(2)RR to produce HCOOH and coupled system for conversion of biomass and its derivatives to produce value-added products.Sn-and Bi-based electrocatalysts are discussed for CO_(2)RR with regards to the structure of the catalyst and reaction mechanisms.Electro-oxidation reactions of biomass derived sugars,alcohols,furan aldehydes and even polymeric components of lignocellulose were reviewed as alternatives to replace oxygen evolution reaction(OER)in the conventional electrolysis process.It was recommended that to further improve the efficiency of the coupled system,future work should be focused on the development of more efficient and stable catalysts,careful design of the electrolytic cells for improving the mass transfer and development of environment-friendly processes for recovering the formed formate and biomass oxidation products.

A review on plasma-based CO_(2) utilization:process considerations in the development of sustainable chemical production

Plasma-based processes,particularly in carbon capture and utilization,hold great potential for addressing environmental challenges and advancing a circular carbon economy.While significant progress has been made in understanding plasma-induced reactions,plasma-catalyst interactions,and reactor development to enhance energy efficiency and conversion,there remains a notable gap in research concerning overall process development.This review emphasizes the critical need for considerations at the process level,including integration and intensification,to facilitate the industrialization of plasma technology for chemical production.Discussions centered on the development of plasma-based processes are made with a primary focus on CO_(2) conversion,offering insights to guide future work for the transition of the technology from laboratory scale to industrial applications.Identification of current research gaps,especially in upscaling and integrating plasma reactors with other process units,is the key to addressing critical issues.The review further delves into relevant research in process evaluation and assessment,providing methodological insights and highlighting key factors for comprehensive economic and sustainability analyses.Additionally,recent advancements in novel plasma systems are reviewed,presenting unique advantages and innovative concepts that could reshape the future of process development.This review provides essential information for navigating the path forward,ensuring a comprehensive understanding of challenges and opportunities in the development of plasma-based CCU process.

Fine-tuning electronic structure of N-doped graphitic carbon-supported Co-and Fe-incorporated Mo_(2)C to achieve ultrahigh electrochemical water oxidation activity

Mo_(2)C is an excellent electrocatalyst for hydrogen evolution reaction(HER).However,Mo_(2)C is a poor electrocatalyst for oxygen evolution reaction(OER).Herein,two different elements,namely Co and Fe,are incorporated in Mo_(2)C that,therefore,has a finely tuned electronic structure,which is not achievable by incorporation of any one of the metals.Consequently,the resulting electrocatalyst Co_(0.8)Fe_(0.2)-Mo_(2)C-80 displayed excellent OER catalytic performance,which is evidenced by a low overpotential of 214.0(and 246.5)mV to attain a current density of 10(and 50)mA cm^(-2),an ultralow Tafel slope of 38.4 mV dec^(-1),and longterm stability in alkaline medium.Theoretical data demonstrates that Co_(0.8)Fe_(0.2)-Mo_(2)C-80 requires the lowest overpotential(1.00 V)for OER and Co centers to be the active sites.The ultrahigh catalytic performance of the electrocatalyst is attributed to the excellent intrinsic catalytic activity due to high Brunauer-Emmett-Teller specific surface area,large electrochemically active surface area,small Tafel slope,and low chargetransfer resistance.

Analysis of Differences in Electrochemical Performance Between Coin and Pouch Cells for Lithium-Ion Battery Applications

Small coin cell batteries are predominantly used for testing lithium-ion batteries(LIBs)in academia because they require small amounts of material and are easy to assemble.However,insufficient attention is given to difference in cell performance that arises from the differences in format between coin cells used by academic researchers and pouch or cylindrical cells which are used in industry.In this article,we compare coin cells and pouch cells of different size with exactly the same electrode materials,electrolyte,and electrochemical conditions.We show the battery impedance changes substantially depending on the cell format using techniques including Electrochemical Impedance Spectroscopy(EIS)and Galvanostatic Intermittent Titration Technique(GITT).Using full cell NCA-graphite LIBs,we demonstrate that this difference in impedance has important knock-on effects on the battery rate performance due to ohmic polarization and the battery life time due to Li metal plating on the anode.We hope this work will help researchers getting a better idea of how small coin cell formats impact the cell performance and help predicting improvements that can be achieved by implementing larger cell formats.

Atomically Dispersed Zinc Active Sites Efficiently Promote the Electrochemical Conversion of N_(2) to NH_(3)

At present,the research on highly active and stable nitrogen reduction reaction catalysts is still challenging work for the electrosynthesis of ammonia(NH_(3)).Herein,we synthesized atomically dispersed zinc active sites supported on N-doped carbon nanosheets(Zn/NC NSs)as an efficient nitrogen reduction reaction catalyst,which achieves a high ammonia yield of 46.62μg h^(-1)mg^(-1)_(cat).at-0.85 V(vs RHE)and Faradaic efficiency of 95.8%at-0.70 V(vs RHE).In addition,Zn/NC NSs present great stability and selectivity,and there is no significant change in NH_(3)rate and Faradaic efficiencies after multiple cycles.The structural characterization shows that the active center in the nitrogen reduction reaction process is the Zn-N_(4)sites in the catalyst.DFT calculation confirms that Zn/NC with Zn-N_(4)configuration has a lower energy barrier for the formation of^(*)NNH intermediate compared with pure N-doped carbon nanosheets(N-C NSs),thus promoting the hydrogenation kinetics in the whole nitrogen reduction reaction process.

Organic geochemical,petrographic and palynological characterization of claystones of the Palaeogene Toraja Formation,and oil seeps in the Enrekang Sub-basin,south Sulawesi,Indonesia:Implications for hydrocarbon source rock potential

An organic geochemical,petrographical,and palynological evaluation was conducted on 30 claystone outcrop samples of the Toraja Formation,along with a geochemical analysis of an oil seep in the Enrekang Sub-basin.The aim of the study was to determine the correlation between oil and source rock in terms of age,depositional environment,organic material sources,and maturity level.The total organic carbon content of the claystone samples varies from 0.03 to 4.52 wt%,which are classified as poor to excellent.The claystones are immature to post-mature with a mixture of TypeⅡandⅢkerogen.Their vitrinite reflectance values range from 0.47 to 4.52%Ro.The samples of Toraja Formation rock and the oil seep source rock might have a similar depositional environment,a deltaic marine depositional setting with high oxidizing conditions.Organic material sources for rock and oil samples are dominated by terrestrial input.The oil is inferred to have originated from the Paleogene source rocks,which correlates in age with the Toraja Formation.The recovered palynomorphs from the studied rock samples suggest a late Eocene to Oligocene age with a strong terrestrial influence of shallow marine depositional setting.The biomarker analysis shows that the rock samples have a more substantial contribution from the terrigenous higher plants,while the oil sample indicates a higher degree of marine influence.The maturity levels are also different between the oil(peak mature)and the analyzed rock samples(immature).It is inferred that the oil seep source rock is equivalent to the analyzed rock sample but more mature,having been deposited under more marine conditions.The oil seep source rock is not exposed and is located in the deeper part of the basin.A deeper marine facies(i.e.distal delta front and prodelta facies)in front of the distributary mouth bar within a delta is interpreted as the source rock of the oil seep sample.

Analysis of combustion characteristics and chemical properties for biocoke fuel

Analyses of the characteristics and properties of biocoke fuel from several biomass wastes were carried out to determine the energy potential of the fuel.Biocoke production in this research uses heating and pressure methods simultaneously under constant conditions.Experimental results using thermogravimetric analysis show that biocoke empty-fruit-bunches(EFB)have a higher energy potential of 26.57 MJ/kg.Meanwhile,mangrove biocoke recorded the lowest ash content at 1.81%compared to EFB at 5.09%.The carbon content of mangrove biocoke is 58.02%,slightly higher than that of EFB,56.70%,but EFB is higher than that of other biomass.Overall,the energy content recorded in biocoke increased significantly compared to raw biomass.

Physicochemical Properties of the Seed Oil of Khaya senegalensis

The physicochemical characteristics of Khaya senegalensis seed oil were investigated. Iodine value, saponification value, percentage free fatty acid (FFA), acid value, and peroxide value were the chemical parameters examined in the oil analysis, while specific gravity and refractive index were examined as physical parameters. The results showed that the acid value was 1.18 ± 0.01, the saponification value was 191.76 ± 0.01 mgKOH/gm, and the iodine value was 102.79 ± 0.01. It contained 0.59 ± 0.01 percent free fatty acid. The value of peroxide was 6.83 ± 0.01 meq/kg. The results showed that the refractive index was 1.462 ± 0.02 and the specific gravity was 0.9194 ± 0.04. The established parameters fell within the worldwide and Nigerian vegetable oil industry standards.

Physicochemical and Thermal Properties of Some Key Tropical Sawdust Woods for Energy Production

In South Saharan countries, 85% of the population uses biomass as a primary energy source. Cameroon presents one of the highest biomass energy and sawmills produce important sawdust resources which are not used and are burnt in piles leading to significant air toxic emissions. Therefore, we have to valorize industrially these available sawdusts. This study focuses on the physicochemical and thermochemical analysis of Ayous, Sapelli and Tali sawdust. The proximate and ultimate analysis, particle size, structural composition, as well as heavy metal content and calorific value were determined. In addition, the thermogravimetric mass losses were also estimated. The results showed that high water contents (24% - 41%) were recorded in the raw sawdust, and the thermal treatment reduced these contents from 78% to values in the range of 4% - 9%. The values for ash and volatile matter content were respectively between 0.25% - 0.74% and 68% - 76%. The LHV is higher in Ayous (17.5 MJ/kg) and Sapelli (16.8 MJ/kg) than that of Tali (15.7 MJ/kg). The concentration of heavy metals is very low in each species. Extractives are more present in Tali (16.06%) than in the other sawdusts. Pyrolysis of sawdust shows the typical decomposition of hemicellulose (270˚C - 325˚C), cellulose (325˚C - 400˚C) and lignin (200˚C - 550˚C) with a maximum loss of 75% at 370˚C and the melting point is 320˚C. The results of the sawdust parameters determined in the paper can be valorized to reduce pollutants emissions by developing the efficiency and effectiveness of biomass energy processes and promoting the use of biomass as a sustainable alternative to traditional fossil fuels.

Physico-Chemical Analysis of Soils Used for Pineapple Cultivation in the Sub-Prefectures of Maferinyah and Friguiagbé (Prefectures of Forécariah and Kindia) Republic of Guinea

Over the years, pineapple production in the Republic of Guinea has become less competitive in the West African sub-region, with a world ranking of 144th. It is therefore only natural to review certain parameters in order to improve this ranking. To do this, certain physico-chemical parameters of soil samples from Friguiagbé and Maferinyah (in the Kindia and Forécariah prefectures) were taken and analysed using the following techniques: Pipette de Robinson, Anne, Bray II, Kapen HICDVITZ, Mc. Lead (1982). The analytical results show that the soils at Friguiagbé in Kindia and Maferinyah in Forécariah are acidic, with pH values of 4.4 and 4.7 (fields I and II) and 4.8 and 4.7 (fields I and II) respectively. The soils have a silty-sandy texture. This study could therefore serve as a guide for the Ministry of Agriculture of the Republic of Guinea.

Study of the Chemical and Mineralogical Composition of Kindia Bauxite in the Republic of Guinea: The Case of the Saföfö Site

The chemical and mineralogical composition of bauxite deposits is a key factor in the profitability of refining processes. The study of bauxites from the Saföfö site has assessed variations in chemical and mineralogical composition under various conditions, as well as the optimum conditions for their exploitation. The methodologies used in this study include experimental methods for determining moisture content, chemical composition, mineralogical composition, and specific density of bauxite. The results show significant variation in moisture content among the bauxite samples, with values ranging from 2.90% to 17.80%. The silica percentages in the samples range from 1.69% to 8.14%, while alumina percentages vary from 36.81% to 54.03%. After calcination, alumina oxide percentages range from 40% to 75%. After chemical activation, alumina oxides Al2O3 range from 40% to over 50%. Gibbsite is the most abundant mineral, accounting for about 60% - 70% of the total composition of the bauxite samples. Samples A to F have bulk densities varying between approximately 3.6 and 3.9. Sample B has the highest density, around 3.9, while sample C has the lowest, at around 3.5. Bauxite mining at the Saföfö site offers significant potential for the alumina industry, provided appropriate processing methods are selected to maximize quality and profitability while minimizing environmental impact.

Green microfluidics in microchemical engineering for carbon neutrality

The concept of“carbon neutrality”poses a huge challenge for chemical engineering and brings great opportunities for boosting the development of novel technologies to realize carbon offsetting and reduce carbon emissions.Developing high-efficient,low-cost,energy-efficient and eco-friendly microfluidicbased microchemical engineering is of great significance.Such kind of“green microfluidics”can reduce carbon emissions from the source of raw materials and facilitate controllable and intensified microchemical engineering processes,which represents the new power for the transformation and upgrading of chemical engineering industry.Here,a brief review of green microfluidics for achieving carbon neutral microchemical engineering is presented,with specific discussions about the characteristics and feasibility of applying green microfluidics in realizing carbon neutrality.Development of green microfluidic systems are categorized and reviewed,including the construction of microfluidic devices by bio-based substrate materials and by low carbon fabrication methods,and the use of more biocompatible and nondestructive fluidic systems such as aqueous two-phase systems(ATPSs).Moreover,low carbon applications benefit from green microfluidics are summarized,ranging from separation and purification of biomolecules,high-throughput screening of chemicals and drugs,rapid and cost-effective detections,to synthesis of fine chemicals and novel materials.Finally,challenges and perspectives for further advancing green microfluidics in microchemical engineering for carbon neutrality are proposed and discussed.

Defect engineering of ternary Cu-In-Se quantum dots for boosting photoelectrochemical hydrogen generation

Heavy-metal-free ternary Cu–In–Se quantum dots(CISe QDs)are promising for solar fuel production because of their low toxicity,tunable band gap,and high light absorption coefficient.Although defects significantly affect the photophysical properties of QDs,the influence on photoelectrochemical hydrogen production is not well understood.Herein,we present the defect engineering of CISe QDs for efficient solar-energy conversion.Lewis acid–base reactions between metal halide–oleylamine complexes and oleylammonium selenocarbamate are modulated to achieve CISe QDs with the controlled amount of Cu vacancies without changing their morphology.Among them,CISe QDs with In/Cu=1.55 show the most outstanding photoelectrochemical hydrogen generation with excellent photocurrent density of up to 10.7 mA cm-2(at 0.6 VRHE),attributed to the suitable electronic band structures and enhanced carrier concentrations/lifetimes of the QDs.The proposed method,which can effectively control the defects in heavy-metal-free ternary QDs,offers a deeper understanding of the effects of the defects and provides a practical approach to enhance photoelectrochemical hydrogen generation.

Overview of emerging catalytic materials for electrochemical green ammonia synthesis and process

The concept of“green-ammonia-zero-carbon emission”is an emerging research topic in the global community and many countries driving toward decarbonizing a diversity of applications dependent on fossil fuels.In light of this,electrochemical nitrogen reduction reaction(ENRR)received great attention at ambient conditions.The low efficiency(%)and ammonia(NH_(3))production rates are two major challenges in making a sustainable future.Besides,hydrogen evolution reaction is another crucial factor for realizing this NH_(3)synthesis to meet the large-scale commercial demand.Herein,the(i)importance of NH_(3)as an energy carrier for the next future,(ii)discussion with ENRR theory and the fundamental mechanism,(iii)device configuration and types of electrolytic systems for NH_(3)synthesis including key metrics,(iv)then moving into rising electrocatalysts for ENRR such as single-atom catalysts(SACs),MXenes,and metal–organic frameworks that were scientifically summarized,and(v)finally,the current technical contests and future perceptions are discussed.Hence,this review aims to give insightful direction and a fresh motivation toward ENRR and the development of advanced electrocatalysts in terms of cost,efficiency,and technologically large scale for the synthesis of green NH_(3).

High throughput screening of single atomic catalysts with optimized local structures for the electrochemical oxygen reduction by machine learning

Single atomic catalysts(SACs),especially metal-nitrogen doped carbon(M-NC)catalysts,have been extensively explored for the electrochemical oxygen reduction reaction(ORR),owing to their high activity and atomic utilization efficiency.However,there is still a lack of systematic screening and optimization of local structures surrounding active centers of SACs for ORR as the local coordination has an essential impact on their electronic structures and catalytic performance.Herein,we systematic study the ORR catalytic performance of M-NC SACs with different central metals and environmental atoms in the first and second coordination sphere by using density functional theory(DFT)calculation and machine learning(ML).The geometric and electronic informed overpotential model(GEIOM)based on random forest algorithm showed the highest accuracy,and its R^(2) and root mean square errors(RMSE)were 0.96 and 0.21,respectively.30 potential high-performance catalysts were screened out by GEIOM,and the RMSE of the predicted result was only 0.12 V.This work not only helps us fast screen high-performance catalysts,but also provides a low-cost way to improve the accuracy of ML models.

High Fe^(LS)(C)electrochemical activity of an iron hexacyanoferrate cathode boosts superior sodium ion storage

Sodium iron hexacyanoferrate(FeHCF)is one of the most promising cathode materials for sodium-ion batteries(SIBs)due to its low cost theoretical capacity.However,the low electrochemical activity of Fe^(LS)(C)in FeHCF drags down its practical capacity and potential plateau.Herein,FeHCF with high Fe^(LS)(C)electrochemical activity(C-FeHCF)is synthesized via a facile citric acid-assisted solvothermal method.As the cathode of SIBs,C-FeHCF shows superior cycling stability(ca.87.3%capacity retention for 1000 cycles at 10 C)and outstanding rate performance(ca.68.5%capacity retention at 50 C).Importantly,the contribution of Fe^(LS)(C)to the whole capacity was quantitatively analyzed via combining dQ/dV and discharge curve for the first time,and the index reaches 44.53%for C-FeHCF,close to the theoretical value.In-situ X-ray diffraction proves the structure stability of C-FeHCF during charge-discharge process,ensuring its superior cycling performance.Furthermore,the application feasibility of the C-FeHCF cathode in quasi-solid SIBs is also evaluated.The quasi-solid SIBs with the C-FeHCF cathode exhibit excellent electrochemical performance,delivering an initial discharge capacity of 106.5 mAh g^(−1) at 5 C and high capacity retention of 89.8%over 1200 cycles.This work opens new insights into the design and development of advanced cathode materials for SIBs and the beyond.

Electrochemical partial reduction of Ni(OH)_(2) to Ni(OH)_(2)/Ni via coupled oxidation of an interfacing NiAl intermetallic compound for robust hydrogen evolution

Ni-based porous electrocatalysts have been widely used in the hydrogen evolution reaction(HER)in alkaline water electrolysis,and the catalysts are produced by selective leaching of Al from Ni-Al alloys.It is well known that chemical leaching of Ni-Al intermetallic compound(IMC)generates a high surface area in Ni(OH)_(2).However,the Ni(OH)_(2) produced by leaching the Ni-Al intermetallic compound retards the hydrogen evolution reaction,which is attributed to its weak hydrogen adsorption energy.In this study,we controlled the chemical state of Ni using plasma vapor deposition(PVD)followed by heat treatment,selective Al leaching,and electrochemical reduction.X-ray diffraction(XRD),scanning microscopy(SEM),transmission electron microscopy(TEM),and energy-dispersive X-ray spectroscopy(EDS)were used to confirm the phase evolution of the electrocatalysts during fabrication.We reveal that the heat-treated Ni-Al alloy with a thick Ni2Al3surface layer underwent selective Al leaching and produced biphasic interfaces comprising Ni(OH)_(2) and NiAl IMCs at the edges of the grains in the outermost surface layer.Coupled oxidation of the interfacing NiAl IMCs facilitated the partial reduction of Ni(OH)_(2) to Ni(OH)_(2)/Ni in the grains during electrochemical reduction,as confirmed by X-ray photoelectron spectroscopy(XPS).An electrocatalyst containing partially reduced Ni(OH)_(2)/Ni exhibited an overpotential of 54 mV at 10 mA/cm^(2) in a half-cell measurement,and a cell voltage of 1.675 V at 0.4 A/cm2for single-cell operation.A combined experimental and theoretical study(density functional theory calculations)revealed that the superior HER activity was attributed to the presence of partially reduced metallic Ni with various defects and residual Al,which facilitated water adsorption,dissociation,and finally hydrogen evolution.

Surface hydrophobic modification of MXene to promote the electrochemical conversion of N_(2) to NH_(3)

Hydrophobic treatment of the catalyst surfaces can suppress the competitive hydrogen evolution reaction(HER) during the nitrogen reduction reaction(NRR).In this work,the surface of Ti_(3)C_(2)Ti_(x) MXene is modified by cetyltrimethylammonium bromide(CTAB) and trimethoxy(3,3,4,4,5,5,6,6,7,7,8,8,8-trideca fluorooctyl) silane(FOTS) to increase the hydrophobicity of MXenes.The ammonia(NH_(3)) production rate and faradaic efficiency(FE) are improved from 37.62 to 54.01 μg h^(-1)mg_(cat)^(-1).and 5.5% to 18.1% at-0.7 V vs.RHE,respectively after surface modification.^(15)N isotopic labeling experiment confirms that nitrogen in produced ammonia originates from N_(2) in the electrolyte.The excellent NRR activity of surface hydrophobic MXenes is mainly due to surfactant molecules,which inhibit the entry of water molecules and the competitive HER,which have been verified by in situ FT-IR,DFT and molecular dynamics calculations.This strategy provides an ingenious method to design more active NRR electrocatalysts.

Catalytic conversion of lignocellulosic biomass into chemicals and fuels

In the search of alternative resources to make commodity chemicals and transportation fuels for a low carbon future,lignocellulosic biomass with over 180-billion-ton annual production rate has been identified as a promising feedstock.This review focuses on the state-of-the-art catalytic transformation of lignocellulosic biomass into value-added chemicals and fuels.Following a brief introduction on the structure,major resources and pretreatment methods of lignocellulosic biomass,the catalytic conversion of three main components,i.e.,cellulose,hemicellulose and lignin,into various compounds are comprehensively discussed.Either in separate steps or in one-pot,cellulose and hemicellulose are hydrolyzed into sugars and upgraded into oxygen-containing chemicals such as 5-HMF,furfural,polyols,and organic acids,or even nitrogen-containing chemicals such as amino acids.On the other hand,lignin is first depolymerized into phenols,catechols,guaiacols,aldehydes and ketones,and then further transformed into hydrocarbon fuels,bioplastic precursors and bioactive compounds.The review then introduces the transformations of whole biomass via catalytic gasification,catalytic pyrolysis,as well as emerging strategies.Finally,opportunities,challenges and prospective of woody biomass valorization are highlighted.

Templated synthesis of transition metal phosphide electrocatalysts for oxygen and hydrogen evolution reactions

Transition metal phosphides(TMPs)have been regarded as alternative hydrogen evolution reaction(HER)and oxygen evolution reaction(OER)catalysts owing to their comparable activity to those of noble metal-based catalysts.TMPs have been produced in various morphologies,including hollow and porous nanostructures,which are features deemed desirable for electrocatalytic materials.Templated synthesis routes are often responsible for such morphologies.This paper reviews the latest advances and existing challenges in the synthesis of TMP-based OER and HER catalysts through templated methods.A comprehensive review of the structure-property-performance of TMP-based HER and OER catalysts prepared using different templates is presented.The discussion proceeds according to application,first by HER and further divided among the types of templates used-from hard templates,sacrificial templates,and soft templates to the emerging dynamic hydrogen bubble template.OER catalysts are then reviewed and grouped according to their morphology.Finally,prospective research directions for the synthesis of hollow and porous TMP-based catalysts,such as improvements on both activity and stability of TMPs,design of environmentally benign templates and processes,and analysis of the reaction mechanism through advanced material characterization techniques and theoretical calculations,are suggested.