Electrocatalytic CO_(2)reduction to syngas

While carbon dioxide(CO_(2))is a major greenhouse gas,it is also an important C1 resource.In the trend of energy conservation and emission reduction,electrocatalytic reduction has become a very promising strategy for CO_(2)utilization because it can convert CO_(2)directly to high-valued chemicals and fuels under mild conditions.In particular,the product CO and by-product H_(2)can be combined into syngas by an electrocatalytic CO_(2)reduction reaction(CO_(2)RR)in an aqueous medium.Different molar ratios of CO and H_(2)may be used to produce essential bulk chemicals or liquid fuels such as methanol,alkanes,and olefins through thermochemical catalysis,Fischer-Tropsch synthesis,microbial fermentation,and other techniques.This work discusses the latest strategies in controlling the molar ratio of CO/H_(2)and improving the yield of CO_(2)RR-to-syngas.The challenges of electrocatalytic syngas production are analyzed from an industrial application perspective,and the possible measures to overcome them are proposed in terms of new catalyst design,electrolyte innovation,flow reactor optimization,anodic reaction coupling,and operando technique application.

Advanced 3D ordered electrodes for PEMFC applications: From structural features and fabrication methods to the controllable design of catalyst layers

The catalyst layers(CLs) electrode is the key component of the membrane electrode assembly(MEA) in proton exchange membrane fuel cells(PEMFCs). Conventional electrodes for PEMFCs are composed of carbon-supported, ionomer, and Pt nanoparticles, all immersed together and sprayed with a micron-level thickness of CLs. They have a performance trade-off where increasing the Pt loading leads to higher performance of abundant triple-phase boundary areas but increases the electrode cost. Major challenges must be overcome before realizing its wide commercialization. Literature research revealed that it is impossible to achieve performance and durability targets with only high-performance catalysts, so the controllable design of CLs architecture in MEAs for PEMFCs must now be the top priority to meet industry goals. From this perspective, a 3D ordered electrode circumvents this issue with a support-free architecture and ultrathin thickness while reducing noble metal Pt loadings. Herein, we discuss the motivation in-depth and summarize the necessary CLs structural features for designing ultralow Pt loading electrodes. Critical issues that remain in progress for 3D ordered CLs must be studied and characterized. Furthermore, approaches for 3D ordered CLs architecture electrode development, involving material design, structure optimization, preparation technology, and characterization techniques, are summarized and are expected to be next-generation CLs for PEMFCs. Finally, the review concludes with perspectives on possible research directions of CL architecture to address the significant challenges in the future.

The newly-assisted catalytic mechanism of surface hydroxyl species performed as the promoter in syngas-to-C2 species on the Cu-based bimetallic catalysts

In the conversion process of syngas-to-C_(2)species,the OH species are inevitably produced accompanying the production of key intermediates CH_(x)(x=1-3),traditionally,the function of surface OH species is generally accepted as the hydrogenating reactive species.This work for the first time proposed and confirmed the assisted catalytic mechanism of surface OH species that performed as the promoter for syngas-to-C_(2)species on Cu-based catalysts.DFT and microkinetic modeling results reveal that the produced OH species accompanying the intermediates CH_(x)production on the MCu(M=Co,Fe,Rh)catalysts can stably exist to form OH/MCu catalysts,on which the presence of surface OH species as the promoter not only presented better activity and selectivity toward CH_(x)(x=1-3)compared to MCu catalysts,but also significantly suppressed CH_(3)OH production,providing enough CH_(x)sources to favor the production of C_(2)hydrocarbons and oxygenates.Correspondingly,the electronic properties analysis revealed the essential relationship between the electronic feature of OH/MCu catalysts and catalytic performance,attributing to the unique electronic micro-environment of the catalysts under the interaction of surface OH species.This new mechanism is called as OH-assisted catalytic mechanism,which may be applied in the reaction systems related to the generation of OH species.

Progress in carbon dioxide separation and capture: A review

This article reviews the progress made in CO2 separation and capture research and engineering. Various technologies, such as absorption, adsorption, and membrane separation, are thoroughly discussed. New concepts such as chemical-looping combustion and hydrate-based separation are also introduced briefly. Future directions are suggested. Sequestration methods, such as forestation, ocean fertilization and mineral carbonation techniques are also covered. Underground injection and direct ocean dump are not covered.

Catalyst design strategies towards highly shape-selective HZSM-5 for paraxylene through toluene alkylation

With the shape selective zeolite catalyst,toluene alkylation with methanol to para-xylene(MTPX)technology could produce highly pure para-xylene(PX)in one step.The lower feedstock cost and less energy consumption in products separation make it more competitive compared to the current toluene disproportionation route.Thus,MTPX is regarded as the most reasonable production route for PX production.This article reviews the strategies that applied to the preparation of high-performance catalysts for MTPX,with special focus on the precise control of pore dimension and acid sites distribution in zeolite to achieve the highest selectivity to PX.The outlook of the MTPX catalyst is also proposed to guide the catalyst development in the field.

Improved methanol synthesis performance of Cu/ZnO/Al_(2)O_(3)catalyst by controlling its precursor structure

Methanol,a versatile chemical,fuel additive and potential H_(2) carrier,has attracted great attention.Despite of the wide industrialization,improvement of Cu-based methanol-synthesis catalysts is highly anticipated.Accordingly,a series of Cu/ZnO/Al_(2)O_(3) with designed precursor structures were prepared,and its structure-function relationship was investigated to make progress on this area.Results showed the catalyst derived from highly zinc-substituted malachite demonstrated the best catalytic performance in this work.It was found that the well-behaved catalyst possessed relatively high Cu specific surface area and exposed Cu concentration,and the well Cu/ZnO synergy.CuZn alloy was found by In-situ XRD tests,and its effect on the catalyst's thermostability was discussed.Fractional precipitation,which facilitated the Cu^(2+) substitution by Zn^(2+) in malachite lattice,could be an efficient preparation method of the Cu/ZnO/Al_(2)O_(3) catalyst.

Direct conversion of methane to methanol by electrochemical methods

A convenient method for methane(CH_(4))direct conversion to methanol(CH_(3)OH)is of great significance to use methane-rich resources,especially clathrates and stranded shale gas resources located in remote regions.Theoretically,the activation of CH_(4) and the selectivity to the CH_(3)OH product are challenging due to the extreme stability of CH_(4) and relatively high reactivity of CH_(3)OH.The state-of-the-art‘methane reforming-methanol synthesis’process adopts a two-step strategy to avoid the further reaction of CH_(3)OH under the harsh conditions required for CH_(4) activation.In the electrochemical field,researchers are trying to develop conversion pathways under mild conditions.They have found suitable catalysts to activate the C–H bonds in methane with the help of external charge and have designed the electrode reactions to continuously generate certain active oxygen species.These active oxygen species attack the activated methane and convert it to CH_(3)OH,with the benefit of avoiding over-oxidation of CH_(3)OH,and thus obtain a high conversion efficiency of CH_(4) to CH_(3)OH.This mini-review focuses on the advantages and challenges of electrochemical conversion of CH4 to CH_(3)OH,especially the strategies for supplying electro-generated active oxygen species in-situ to react with the activated methane.

Removal of ions from produced water using Powder River Basin coal

In addition to being used as an energy source,coal also has significant potential for other,more sustainable uses including water treatment.In this study,we present a simple approach to treat water that was produced during oil production and contained a total dissolved solids(TDS)content of over 150 g/L using Powder River Basin(PRB)coal.PRB coal used as packing material in a flow-through column effectively removed 60%–80%of the cations and anions simultaneously.Additionally,71%–92%of the total organic carbon in the produced water was removed as was all of the total suspended solids.The removal mechanisms of both cations and anions were investigated.Cations were removed by ion exchange with protons from oxygen-containing functional groups such as carboxylic and phenolic hydroxyl groups.Anions,mainly Cl−1,appeared to be removed through either the formation of resonance structures as a result of delocalization of electrons within coal molecules or through ion–πinteractions.We propose that coal is a“pseudo-amphoteric”exchange material that can remove cations and anions simultaneously by exchanging ions with both ionized and non-ionized acids that are ubiquitous in coal structure or resonance effect.

Enhanced near-zero-CO2-emission chemicals-oriented oil production from coal with inherent CO2 recycling: Part I—PRB coal fast pyrolysis coupled with CO2/CH4 reforming

In this study,the Powder River Basin(PRB)coal fast pyrolysis was conducted at 700°C in the atmosphere of syngas produced by CH4-CO2 reforming in two different patterns,including the double reactors pattern(the first reactor is for syngas production and the second is for coal pyrolysis)and double layers pattern(catalyst was at upper layer and coal was at lower layer).Besides,pure gases atmosphere including N2,H2,CO,H2-CO were also tested to investigate the mechanism of the coal pyrolysis under different atmospheres.The pyrolysis products including gas,liquid and char were characterized,the result showed that,compared with the inert atmosphere,the tar yield is improved with the reducing atmospheres,as well as the tar quality.The hydrogen partial pressure is the key point for that improvement.In the atmosphere of H2,the tar yield was increased by 31.3%and the contained BTX(benzene,toluene and xylene)and naphthalene were increased by 27.1%and 133.4%.The double reactors pattern also performed outstandingly,with 25.4%increment of tar yield and 25.0%and 79.4%for the BTX and naphthalene.The double layers pattern is not effective enough due to the low temperature(700°C)in which the Ni-based catalyst was not fully activated.

C_(2)H_(2)semi-hydrogenation on the Pd_(x)M_(y)cluster/graphdiyne catalysts:Effects of cluster composition and size on the activity and selectivity

C_(2)H_(2)semi-hydrogenation has been widely applied in industry to eliminate trace C_(2)H_(2)from C_(2)H_(4)feed.C_(2)H_(2)semi-hydrogenation to C_(2)H_(4)on a series of the newly designed catalysts,graphdiyne(GDY)as a new carbon allotrope supported different sizes of Pd_(x)M_(y)clusters(Pd_(x)M_(y)/GDY,M=Cu,Ag,Au,Ni;x+y=1-3),were studied using DFT calculations.The results found that C_(2)H_(2)semi-hydrogenation to C_(2)H_(4)on Pd_(x)M_(y)/GDY catalysts exhibits that both the activity and selectivity greatly depend on the composition and size of Pd_(x)M_(y)/GDY catalysts.Surprisingly,our results for the first time discovered the Pd_(1)/GDY catalyst with GDY supported the single atom Pd that presents the best selectivity and activity toward C_(2)H_(4)formation compared to the previously reported catalysts so far in C_(2)H_(2)semi-hydrogenation.This study would provide a theoretical clue for designing and screening out the potential catalysts with GDY supported small sizes of Pd_(x)M_(y)and other metal clusters in C_(2)H_(2)hydrogenation.

Constructing extrinsic oxygen vacancy on the surface of photocatalyst as CO_(2)and electrons reservoirs to improve photocatalytic CO_(2)reduction activity

Constructing own oxygen vacancies in the photocatalysts is a very promising method to improve their photocatalytic CO_(2)reduction activity.However,some catalysts have excellent stabilities,making it difficult for them to construct their own oxygen vacancies.To simplify the above difficulty of stable photocatalysts,constructing extrinsic oxygen vacancies on their surface as a novel idea is proposed.Here,a stable TiO_(2)nanosheet is chosen as a research object,we uniformly deposited BiOCl quantum dots on their surface via a simple adsorption-deposition method.It is found that BiOCl quantum dots are able to simultaneously self-transform into defective BiOCl with many oxygen vacancies when the photocatalyst is performed photocatalytic CO_(2)reduction.These extrinsic oxygen vacancies can act as“CO_(2)and photo-generated electrons reservoirs”to improve CO_(2)capture and accelerate the separation of photogenerated electrons and holes.For the above reasons,the modified TiO_(2)showed obvious enhancement of photocatalytic CO_(2)reduction compared to pristine TiO_(2)and BiOCl.This work may open a new avenue to broaden the use of oxygen vacancies in the process of photocatalytic CO_(2)reduction.

Ethane dehydrogenation over the g-C_(3)N_(4)supported metal singleatom catalysts to enhance reactivity and coking-resistance ability

Ethane dehydrogenation(EDH)to produce ethylene requires high operating temperature to achieve satisfactory ethylene yield,however,this process leads to coke formation and catalyst deactivation.Here,an active site isolation strategy was employed to inhibit side reaction and coke formation over fifteen types of metal single-atom metal/graphitic carbon nitride(M/g-C_(3)N_(4))catalysts.Density functional theory(DFT)calculations completely describe reaction network of ethane dehydrogenation.Onlattice kinetic Monte Carlo simulations were carried out to evaluate catalytic performance under the realistic conditions.The Co/g-C_(3)N_(4),Rh/g-C_(3)N_(4),Ni/g-C_(3)N_(4)catalysts were screened out to exhibit higher C_(2)H_(4)(g)formation activity and C_(2)H_(4)(g)selectivity close to or equal to 100%.The low reactant partial pressure 0%–5%at atmospheric pressure facilitates ethane dehydrogenation,and the appropriate temperatures over Co/g-C_(3)N_(4),Rh/g-C_(3)N_(4),Ni/g-C_(3)N_(4)catalysts are 673.15,723.15,723.15 K,respectively.Especially,Co/g-C_(3)N_(4)catalyst presents the highest C_(2)H_(4)(g)formation activity,attributing to the appropriate antibonding strength between C atom and metal single-atom.Further,a simple descriptor,the reaction energy of C_(2)H_(5)*dehydrogenation to C_(2)H_(4)*,was proposed to quantitatively and quickly evaluate C_(2)H_(4)(g)formation activity.The present study laid a solid foundation for efficient design and development of single-atom catalysts with high-performance for selective dehydrogenation of alkanes.

Visible-light-induced photocatalytic CO_(2)reduction over zirconium metal organic frameworks modified with different functional groups

The reduction of CO_(2)into high value-added chemicals and fuels by a photocatalytic technology can relieve energy shortages and the environmental problems caused by greenhouse effects.In the current work,an amino-functionalized zirconium metal organic framework(Zr-MOF)was covalently modified with different functional groups via the condensation of Zr-MOF with 2-pyridinecarboxaldehyde(PA),salicylaldehyde(SA),benzaldehyde(BA),and trifluoroacetic acid(TA),named Zr-MOF-X(X=PA,SA,BA,and TA),respectively,through the post-synthesis modification.Compared with Zr-MOF and Zr-MOF-TA,the introduction of PA,SA,or BA into the framework of Zr-MOF can not only enhance the visible-light harvesting and CO_(2)capture,but also accelerate the photogenerated charge separation and transfer,thereby improving the photocatalytic ability of Zr-MOF for CO_(2)reduction.These results indicate that the modification of Zr-MOF with electron-donating groups can promote the photocatalytic CO_(2)reduction.Therefore,the current work provides an instructive approach to improve the photocatalytic efficiency of CO_(2)reduction through the covalent modification of MOFs.

Removal of tetracycline from water by Fe-Mn binary oxide

Significant concerns have been raised over the presence of antibiotics including tetracyclines in aquatic environments.A series of FeMn binary oxide with different Fe：Mn molar ratios was synthesized by a simultaneous oxidation and coprecipitation process for TC removal.Results showed that Fe-Mn binary oxide had higher removal efficiency than that of hydrous iron oxide and hydrous manganese oxide,and that the oxide with a Fe：Mn molar ratio of 5：1 was the best in removal than other molar ratios.The tetracycline removal was highly pH dependent.The removal of tetracycline decreased with the increase of initial concentration,but the absolute removal quantity was more at high concentration.The presence of cations and anions such as Ca2＋,Mg2＋,CO32-and SO42-had no significant effect on the tetracycline removal in our experimental conditions,while SiO32-and PO43-had hindered the adsorption of tetracycline.The mechanism investigation found that tetracycline removal was mainly achieved by the replacement of surface hydroxyl groups by the tetracycline species and formation of surface complexes at the water/oxide interface.This primary study suggests that Fe-Mn binary oxide with a proper Fe：Mn molar ratio will be a very promising material for the removal of tetracycline from aqueous solutions.

Rare earth elements of fly ash from Wyoming’s Powder River Basin coal

The advancement and increasing interests in green energy production and environmental protection technologies have spurred the demand for rare earth elements.On the other hand,the U.S.has to rely 100% on import of these materials as the industry was crashed because of the environmental issues associated with mining and processing,and more importantly lack competitiveness.As rare earth elements have many applications in defense and national security sectors,some of the elements were listed as strategic materials or critical materials because of the uncertainties in supply and prices.Therefore,it has become imperative in searching for alternative resources for supplying rare earth elements including unconventional resources.With the strong incentive,coal fly ash is identified as one of the candidates among them.In this study,we present rare earth element data for the 42 ash samples(all derived from Powder River Basin coal) that we collected from seven states(UT,WY,10,WI,ND,CO,and MI) representing 158 million tons of fly ash.The results indicate scattered distributions of rare earth elements with concentration ranging from 156 to 590 ppm although all the ash samples originated from the same coal basin(Powder River Basin).The rare earth element resource in these ashes is estimated between 74000 and 106000 t.The ash samples were also characterized by elemental analysis,XRD,SEM-EDS and BET surface area.The characterizations of the ashes were discussed as they might have implications in the subsequent rare earth element extraction processes.In summary,fly ash may represent a potential resource for rare earth element production.

Evaluation of natural goethite on the removal of arsenate and selenite from water

Elevated arsenic and selenium concentrations in water cause health problems to both humans and wildlife. Natural and anthropogenic activities have caused contamination of these elements in waters worldwide, making the development of efficient cost-effective methods in their removal essential. In this work, removal of arsenate and selenite from water by adsorption onto a natural goethite(α-FeO OH) sample was studied at varying conditions. The data was then compared with other arsenate, selenite/goethite adsorption systems as much of literature shows discrepancies due to varying adsorption conditions. Characterization of the goethite was completed using inductively coupled plasma mass spectrometry, X-ray diffraction, Fouriertransform infrared spectroscopy, scanning electron microscopy, and Brunauer–Emmett–Teller surface area analysis. Pseudo-first order(PFO) and pseudo-second order(PSO) kinetic models were applied; including comparisons of different regression methods. Various adsorption isotherm models were applied to determine the best fitting model and to compare adsorption capacitates with other works. Desorption/leaching of arsenate and selenite was studied though the addition of phosphate and hydroxyl ions. Langmuir isotherm modeling resulted in maximum adsorption capacities of 6.204 and 7.740 mg/g for arsenate and selenite adsorption,respectively. The PSO model applied with a non-linear regression resulted in the best kinetic fits for both adsorption and desorption of arsenate and selenite. Adsorption decreased with increasing pH. Phosphate induced desorption resulted in the highest percentage of arsenate and selenite desorbed, while hydroxide induced resulted in the fastest desorption kinetics.

Long-term joint effect of nutrients and temperature increase on algal growth in Lake Taihu,China

To study how global warming and eutrophication affect water ecosystems, a multiplicative growth Monod model, modified by incorporating the Arrhenius equation, was applied to Lake Taihu to quantitatively study the relationships between algal biomass and both nutrients and temperature using long-term data. To qualitatively assess which factor was a limitation of the improved model, temperature variables were calculated using annual mean air temperature （AT）, water temperature （WT）, and their average temperature （ST）, while substrate variables were calculated using annual mean total nitrogen （TN）, total phosphorus （TP）, and their weighted aggregate （R）, respectively. The nine fitted curves showed that TN and AT were two important factors influencing algal growth; AT limited growth as algal photosynthesis is mainly carried out near the water surface; N leakage of phytoplankton and internal phosphorus load from sediment explains why TN was the best predictor of peak biomass using the Monod model. The fitted results suggest that annual mean algal biomass increased by 0.145 times when annual mean AT increased by 1.0℃. Results also showed that the more eutrophic the lake, the greater the effect AT had on algal growth. Subsequently, the long-term joint effect of annual temperature increase and eutrophication to water ecosystems can be quantitatively assessed and predicted.

Rare earth elements:Properties and applications to methanol synthesis catalysis via hydrogenation of carbon oxides

Methanol （CH3OH） is an important industrial chemical with a wide variety of uses. Industrial methanol synthesis catalysts are typically composed of Cu, Zn, and AI, but the use of catalysts incorporating rare earth elements has been shown to improve the catalytic performance. Due to their unique chemical and physical properties, the use of rare earth elements （scandium, yttrium, and the lanthanides） in catalysis in general has continued to increase over the past few decades, while the use of rare earth in methanol synthesis catalysts has not, despite often improving pertbrmance. The ability of several of the rare earth elements （Pr, Ce, Eu, Tb, Yb） to easily switch between oxidation states makes them beneficial for many different types of catalysts. However, for methanol synthesis the surface basicity is an important property, and the basic nature of the rare earth elements can be used to tune the basicity of catalysts. A small number of correlations between rare earth properties and catalytic performance have been observed, but often do not apply to other catalysts. Properties such as strength of basic sites, ionic radius, and etec- tronegativity have been found to correlate with performance results such as activity or selectivity.

Review of the progress in preparing nano TiO_2: An important environmental engineering material

TiO2 nanomaterial is promising with its high potential and outstanding performance in photocatalytic environmental applications, such as CO2 conversion, water treatment, and air quality control. For many of these applications, the particle size, crystal structure and phase, porosity, and surface area influence the activity of TiO2 dramatically. TiO2 nanomaterials with special structures and morphologies, such as nanospheres, nanowires, nanotubes, nanorods, and nanoflowers are thus synthesized due to their desired characteristics. With an emphasis on the different morphologies of TiO2 and the influence factors in the synthesis, this review summarizes fourteen TiO2 preparation methods, such as the sol-gel method, solvothermal method, and reverse micelle method. The TiO2 formation mechanisms, the advantages and disadvantages of the preparation methods, and the photocatalytic environmental application examples are proposed as well.

Application of percarbonate and peroxymonocarbonate in decontamination technologies

Sodium percarbonate(SPC)and peroxymonocarbonate(PMC)have been widely used in modified Fenton reactions because of their multiple superior features,such as a wide pH range and environmental friendliness.This broad review is intended to provide the fundamental information,status and progress of SPC and PMC based decontamination technologies according to the peer-reviewed papers in the last two decades.Both SPC and PMC can directly decompose various pollutants.The degradation efficiency will be enhanced and the target contaminants will be expanded after the activation of SPC and PMC.The most commonly used catalysts for SPC activation are iron compounds while cobalt composi-tions are applied to activate PMC in homogenous and heterogeneous catalytical systems.The generation and participation of hydroxyl,superoxide and/or carbonate radicals are involved in the activated SPC and PMC system.The reductive radicals,such as carbon dioxide and hydroxyethyl radicals,can be generated when formic acid or methanol is added in the Fe(II)/SPC system,which can reduce target contaminants.SPC can also be activated by energy,tetraacetylethylenediamine,ozone and buffered alkaline to generate different reactive radicals for pollutant decomposition.The SPC and activated SPC have been assessed for application in-situ chemical oxidation and sludge dewatering treatment.The challenges and prospects of SPC and PMC based decontamination technologies are also addressed in the last section.