CO_(2)-assisted oxidation dehydrogenation of light alkanes over metal-based heterogeneous catalysts

Light olefins are important platform feedstocks in the petrochemical industry,and the ongoing global economic development has driven sustained growth in demand for these compounds.The dehydrogenation of alkanes,derived from shale gas,serves as an alternative olefins production route.Concurrently,the target of realizing carbon neutrality promotes the comprehensive utilization of greenhouse gas.The integrated process of light alkanes dehydrogenation and carbon dioxide reduction(CO_(2)-ODH)can produce light olefins and realize resource utilization of CO_(2),which has gained wide popularity.With the introduction of CO_(2),coke deposition and metal reduction encountered in alkanes dehydrogenation reactions can be effectively suppressed.CO_(2)-assisted alkanes dehydrogenation can also reduce the risk of potential explosion hazard associated with O_(2)-oxidative dehydrogenation reactions.Recent investigations into various metal-based catalysts including mono-and bi-metallic alloys and oxides have displayed promising performances due to their unique properties.This paper provides the comprehensive review and critical analysis of advancements in the CO_(2)-assisted oxidative dehydrogenation of light alkanes(C2-C4)on metal-based catalysts developed in recent years.Moreover,it offers a comparative summary of the structural properties,catalytic activities,and reaction mechanisms over various active sites,providing valuable insights for the future design of dehydrogenation catalysts.

Recent Advances in Transition Metal-Based Catalysts for Electrocatalytic Nitrate Reduction Reaction

The accumulation of excessive nitrate in the atmosphere not only jeopardizes human health but also disrupts the balance of the nitrogen cycle in the ecosystem.Among various nitrate removal technologies,electrocatalytic nitrate reduction reaction(eNO_(3)RR)has been widely studied for its advantages of being eco-friendly,easy to operate,and controllable under environmental conditions with renewable energy as the driving force.Transition metal-based catalysts(TMCs)have been widely used in electrocatalysis due to their abundant reserves,low costs,easy-to-regulate electronic structure and considerable electrochemical activity.In addition,TMCs have been extensively studied in terms of the kinetics of the nitrate reduction reaction,the moderate adsorption energy of nitrogen-containing species and the active hydrogen supply capacity.Based on this,this review firstly discusses the mechanism as well as analyzes the two main reduction products(N_(2)and NH_(3))of eNO_(3)RR,and reveals the basic guidelines for the design of efficient nitrate catalysts from the perspective of the reaction mechanism.Secondly,this review mainly focuses on the recent advances in the direction of eNO_(3RR)with four types of TMCs,Fe,Co,Ni and Cu,and unveils the interfacial modulation strategies of Fe,Co,Ni and Cu catalysts for the activity,reaction pathway and stability.Finally,reasonable suggestions and opportunities are proposed for the challenges and future development of eNO_(3)RR.This review provides far-reaching implications for exploring cost-effective TMCs to replace high-cost noble metal catalysts(NMCs)for eNO_(3)RR.

Recent progress and challenges in structural construction strategy of metal-based catalysts for nitrate electroreduction to ammonia

Ammonia plays an essential role in human production and life as a raw material for chemical fertilizers.The nitrate electroreduction to ammonia reaction(NO_(3)RR)has garnered attention due to its advantages over the Haber-Bosch process and electrochemical nitrogen reduction reaction.Therefore,it represents a promising approach to safeguard the ecological environment by enabling the cycling of nitrogen species.This review begins by discussing the theoretical insights of the NO_(3)RR.It then summarizes recent advances in catalyst design and construction strategies,including alloying,structure engineering,surface engineering,and heterostructure engineering.Finally,the challenges and prospects in this field are presented.This review aims to guide for enhancing the efficiency of electrocatalysts in the NO_(3)RR,and offers insights for converting NO_(3)-to NH_(3).

Performance of Adsorbents for NO_(2) in Furnace Flue Gas

To meet the emission standard of nitrogen oxides(NOx)in the flue gas of batch furnaces through dry adsorption,a calcium-silica inorganic adsorbent was prepared with limestone and quartz as raw materials.Sample Cu-BTC 1#was obtained by solvothermal synthesis,drying and purification in vacuum at 120℃using trimesic acid(H3BTC)and copper nitrate trihydrate(Cu(NO_(3))2·3H_(2)O)as raw materials;likewise,sample Cu-BTC 3#was obtained at 200℃.Sample Cu-BTC 2#was obtained by hydrothermal synthesis,drying and purification in air(metal-organic frameworks,1,3,5-benzene tricarboxylic acid copper).The two types of materials were tested in terms of the NO_(2) adsorption,and then the specific surface area,pore volume,NO_(2) adsorption performance,phase composition,microstructure and thermal stability of the adsorbent materials were exploredvia N_(2) physical adsorption-desorption,SEM,XRD and TG characterization.The results show that:(1)the Cu-BTC samples have higher adsorption capacity than the calcium-silica adsorbent,in which sample Cu-BTC 3#has the largest specific surface area and pore volume,thus adsorption capacity for NO_(2);(2)the calcium-silica adsorbent has better thermal stability and lower total mass loss during the entire process than the Cu-BTC samples;sample Cu-BTC 2#has the best thermal stability among the three Cu-BTC samples,and the metal Cu active sites of the Cu-BTC samples can be exposed at least above 150℃.

Deciphering the linear relationship in the activity of the oxygen reduction reaction on Pt electrodes:A decisive role of adsorbates

Despite substantial efforts in developing high-performance catalysts for the oxygen reduction reaction(ORR),the persistent challenge lies in the high onset overpotential of the ORR,and the effect of the elec-trolyte solution cannot be ignored.Consequently,we have systematically investigated the impact of adsorbate species and concentration,as well as solution pH,on the ORR activity on Pt(111)and Pt(poly)electrodes.The results all tend to establish a linear quantitative relationship between the onset potential for ORR and the adsorption equilibrium potential of the adsorbate.This finding indicates the decisive role of adsorbates in the onset potential for ORR,suggesting that the adsorption potential of adsorbates can serve as an intuitive criterion for ORR activity.Additional support for this conclusion is derived from experimental results obtained from the oxygen evolution reaction on Pt(poly)with different adsorbate species and from the hydrogen evolution reaction on Pt(111)with iodine adsorption.We further propose both an empirical equation for the onset potential for ORR and the concept of a potential-regulated adsor-bate shielding effect to elucidate the influence of adsorbates on ORR activity.This study provides new insights into the high onset overpotential of the ORR and offers potential strategies for predicting and enhancingORRactivity inthefuture.

A functionalized activated carbon adsorbent prepared from waste amidoxime resin by modifying with H_(3)PO_(4) and ZnCl_(2) and its excellent Cr(Ⅵ)adsorption

With the application of resins in various fields, numerous waste resins that are difficult to treat have been produced. The industrial wastewater containing Cr(Ⅵ) has severely polluted soil and groundwater environments, thereby endangering human health. Therefore, in this paper, a novel functionalized mesoporous adsorbent PPR-Z was synthesized from waste amidoxime resin for adsorbing Cr(Ⅵ). The waste amidoxime resin was first modified with H3PO4 and ZnCl_(2), and subsequently, it was carbonized through slow thermal decomposition. The static adsorption of PPR-Z conforms to the pseudo-second-order kinetic model and Langmuir isotherm, indicating that the Cr(Ⅵ) adsorption by PPR-Z is mostly chemical adsorption and exhibits single-layer adsorption. The saturated adsorption capacity of the adsorbent for Cr(Ⅵ) could reach 255.86 mg/g. The adsorbent could effectively reduce Cr(Ⅵ) to Cr(Ⅲ) and decrease the toxicity of Cr(Ⅵ) during adsorption. PPR-Z exhibited Cr(Ⅵ) selectivity in electroplating wastewater. The main mechanisms involved in the Cr(Ⅵ) adsorption are the chemical reduction of Cr(Ⅵ) into Cr(Ⅲ) and electrostatic and coordination interactions. Preparation of PPR-Z not only solves the problem of waste resin treatment but also effectively controls Cr(Ⅵ) pollution and realizes the concept of “treating waste with waste”.

Recent developments and consideration issues in solid adsorbents for CO_2 capture from flue gas

The increase in energy demand caused by industrialization leads to abundant CO_2 emissions into atmosphere and induces abrupt rise in earth temperature. It is vital to acquire relatively simple and cost-effective technologies to separate CO_2 from the flue gas and reduce its environmental impact. Solid adsorption is now considered an economic and least interfering way to capture CO_2, in that it can accomplish the goal of small energy penalty and few modifications to power plants. In this regard, we attempt to review the CO_2 adsorption performances of several types of solid adsorbents, including zeolites, clays, activated carbons, alkali metal oxides and carbonates, silica materials, metal–organic frameworks, covalent organic frameworks, and polymerized high internal phase emulsions. These solid adsorbents have been assessed in their CO_2 adsorption capacities along with other important parameters including adsorption kinetics, effect of water, recycling stability and regenerability. In particular,the superior properties of adsorbents enhanced by impregnating or grafting amine groups have been discussed for developing applicable candidates for industrial CO_2 capture.

Organobentonites as adsorbents for some organic pollutants and its application in wastewater treatment

Two organobentonites were synthesized by placing quaternary ammonium cationscetyltrimethylammonium bromide (CTMAB) and cetylpyridinium chloride (CPC) on bentonite bycation exchange. Their ability to adsorb phenol, aniline. nitrobenzene and p-nitrophenol were examined.The optimal conditions for organobentonites to remove the organic pollutants from waterwere studied. The removal rates for organobentonites to treat the organic compounds in water werefound to be over 8 times for the original mineral (untreated bentonite).The removal rates of organic pollutants and COD of wastewater were further improved by organobentonites in the presence of aluminum sulfate. The structure of organobentonites and the mechanism for their adsorption were investigated by X-ray diffraction (XRD) analysis, infrared spectra and BET surface area.

Highly Selective Lithium Ion Adsorbents:Polymeric Porous Microsphere with Crown Ether Groups

In this study, we prepared and applied polymeric porous microsphere adsorbents with selectivity for Li^+ extraction from aqueous solution. We synthesized the adsorbents by suspension polymerization using methacryloyoxyme-12-crown-4(M12C4) as a functional monomer, which had been synthesized from 2-hyroxymethyl-12-crown-4 and methacryloyl chloride. We verified the chemical composition by solid nuclear magnetic resonance(13C-NMR) spectroscopy and observed the porous structure by scanning electron microscopy(SEM). We conducted adsorption isothermal and kinetic tests to determine the adsorption properties. It was found that the adsorbents showed high adsorption efficiency and an adsorption equilibrium time of 200 min. In addition, since the crown ether used in this work could form a stable complex with Li^+, we observed good selectivity for Li^+ in the prepared solution compared with other ions such as Na^+, K^+, Mg^(2+), and Ca^(2+). We reused the adsorbents five times with no significant decrease in adsorptive capacity.

Adsorption thermodynamics and kinetic investigation of aromatic amphoteric compounds onto different polymeric adsorbents

The adsorption behavior ofp-aminobenzoic acid and o-aminobenzoic acid onto the different polymeric adsorbents was systematically investigated as a function of the solution concentration and temperature. Experimental results indicated that the equilibrium adsorption data of the four polymeric adsorbents fitted well in the Freundlich isotherm. The adsorption capacity of multi-functional polymeric adsorbent NJ-99 was the highest, which might be attributed to the strong hydrogen-bonding interaction between the amino groups on the resin and the carboxyl group of aminobenzoic acid. The adsorption capacity of o-aminobenzoic acid onto any adsorbent was higher than p-aminobenzoic acid. Thermodynamic studies suggested the exothermic, spontaneous physical adsorption process. Adsorption kinetics results showed that the adsorption followed the pseudo-second-order kinetics model and the intraparticle mass transfer process was the rate-controlling step.

Thermodynamic study of adsorption of phenolic compounds onto Amberlite XAD-4 polymeric adsorbents and its acetylized derivative MX-4

Adsorption equilibrium isotherms of phenolic compounds, phenol, p cresol, p chlorophenol and p nitrophenol, from aqueous solutions by Amberlite XAD 4 polymeric adsorbent and its acetylized derivative MX 4 within temperature range of 283 323K were obtained and fitted to the Freundlich isotherms. The capacities of equilibrium adsorption for all four phenolic compounds from their aqueous solutions increased around 20% on the acetylized resin, which may be contributed to the specific surface area and the partial polarity on the network. Estimations of the isosteric enthalpy, free energy, and entropy for the adsorption process were reported.

STUDY ON THE THERMODYNAMIC PROPERTIES OF ADSORPTION OF ETHYL BENZOATE AND DIETHYL PHTHALATE BY PHENOLIC RESIN ADSORBENTS

This paper presents experimental observations on the adsorption of individual solutes by a simple thermodynamic framework, and the equilibrium adsorption of ethyl benzoate and diethyl phthalate on phenolic resin adsorbent in hexane solutions within the temperature range of 293-313 K. The experimental results show that the Freundlich adsorption law is applicable to the adsorption of ethyl benzoate and diethyl phthalate on the adsorbent, since all the correlative factors R' are larger than 0.99. The negative values of all the isosteric adsorption enthalpies for ethyl benzoate and diethyl phthalate indicate that they undergo exothermic processes, while their magnitudes (19-28 kJ/mol) manifest a hydrogen bonding sorption process. Other thermodynamic properties: the free energy changes and the entropy change associated with the adsorption have been calculated from the Gibbs adsorption equation and the Gibbs-Helmholtz equation

ADSORPTION BEHAVIOR OF PHENOLIC COMPOUNDS ONTO POLYMERIC ADSORBENTS MODIFIED WITH 2-CARBOXYBENZOYL GROUPS

Two hypercrosslinked polymeric adsorbents （ZH-01 and Amberlite XAD-4 resin） were employed to remove three kinds of phenolic compounds including phenol, 4-nitrophenol and 2,4-dinitrophenol from aqueous solutions. The study was focused on the static equilibrium adsorption behavior, the column dynamic adsorption and desorption profiles. The Freundlich model gave a perfect fitting to the isotherm data. The adsorbing capacities for these three compounds on ZH-01 were higher than those on Amberlite XAD-4 within the temperature range 288-318 K, which was attributed to the large micropore area and 2-carboxybenzoyl functional groups on the network of ZH-01 resin. The adsorption for phenol and 4- nitrophenol on ZH-01 was a physical adsorption process, while for 2,4-dinitrophenol it was a coexistence process of physical adsorption and chemisorption＇s transitions. The column test showed the advantages of ZH-01 in the dynamic adsorption processes of phenolic compounds. Being used as the desorption reagent, sodium hydroxide solution showed an excellent performance.

Effects of the surface chemistry of macroreticular adsorbents on the adsorption of 1-naphthol/1-naphthylamine mixtures from water

The adsorption behaviors of 1-naphthol, 1-naphthylamine and l-naphthol/l-naphthylamine mixtures in water over two macroreticular adsorbents were investigated in single or binary batch systems at 293 K, 303 K and 313 K respectively. All the adsorption isotherms in the studied systems can be adequately fitted by Langmuir model. In the case of aminated macroreticular adsorbent NDA103, 1-naphthol is adsorbed to a larger extent than 1-naphthylamine; while, the opposite trend is found for nonpolar macroreticular adsorbent NDA100. It is noteworthy that at higher temperature（303 K and 313 K）, the total uptake amounts of 1-naphthol and 1-naphthylamine in all binary-component systems are obvious larger than the pure uptake amounts in single-component systems, which is presumably due to the cooperative effect primarily arisen from the hydrogen-bonding interaction between the loaded 1-naphthol and 1-naphthylamine molecules. The simultaneous adsorption systems were confirmed to be helpful to the selective adsorption towards 1-naphthol according to the larger selective index.

Binding Capacity for Aflatoxin B_1 by Different Adsorbents

In this article, in vitro adsorption of aflatoxin B1 （AFB1） onto different adsorbents was characterized and the result was verified by comparing the growth performance and serum protein levels of broilers exposed to aflatoxin-contamination feed. Main components of adsorbents selected were yeast cell extracts （Product A）, HSCAS （Product B）, and a mixture of yeast product and HSCAS （Product C）, respectively. A total of 240 broilers were assigned to eight treatments, and the effects of three types of adsorbents on growth performance and serum protein levels were evaluated. Results indicated that Product B had the highest in vitro affinity for AFB1, followed by Product C and Product A. Product B bound 97.69% of the AFB1 in solution in 10 min, and it remained over 96.03% in 60 min at pH 8.0. The B-AFB1 complex was much stronger than the other two complexes in vitro condition （P 〈 0.05）. Feed intake （FI） and average daily gain （ADG） decreased （P 〈 0.05） and feed gain ratio increased （P 〈0.05） in the treatment fed aflatoxin-contaminated feed versus treatment on the basal feed. Serum total protein （TP）, albumin （ALB）, and globulin （GLOB） levels were significantly decreased （P〈0.05）. Product B （0.15%） increased growth performance and improved serum protein levels, Product A and Product C were not as effective as Product B. Three adsorbents tested here had sufficient potential to AFBt in some extents and Product B could bind AFB1 more effectively than Product A and Product C. These results indicated that Product B could alleviate some of the AFBt toxic effect in broilers.

Carbonaceous Adsorbents Prepared from Sewage Sludge and Its Application for Hg^0 Adsorption in Simulated Flue Gas

The carbonaceous adsorbent was prepared from mixtures of dewatered sludge and sawdust with enhanced ZnCl2 chemical activation.Characteristics of the adsorbent were studied using scanning electron microscope(SEM) ,Fourier transform infrared spectroscopy(FT-IR) ,and adsorption of nitrogen.The surface analysis showed that the carbonaceous adsorbent had good specific surface and porosity(394 m 2 ·g-1of BET surface,0.12 and 0.10 ml·g-1of microporous and mesoporous volume,respectively) .The oxygen functional groups such as OH,C O and C O were found on the surface by FTIR and XPS(X-ray photoelectron spectroscopy) .The adsorption of elemental mercury(Hg0) on the carbonaceous adsorbent was studied in a fixed bed reactor.The dynamic adsorption capacity of carbonaceous adsorbent increased with influent mercury concentration,from 23.6μg·g-1at 12.58μg·m-3to 87.9μg·g-1at 72.50μg·m-3,and decreased as the adsorption temperature increased,from 246 μg·g-1 at 25°C to 61.3μg·g-1 at 140°C,when dry nitrogen was used as the carrier gas.The carbonaceous adsorbent presented higher dynamic adsorption capacity than activated carbon,which was 81.2μg·g-1and 53.8μg·g-1respectively.The adsorption data were fitted to the Langmuir adsorption model.The physical and chemical adsorption were identified on the adsorbent.

Electrodeposition:Synthesis of advanced transition metal-based catalyst for hydrogen production via electrolysis of water

Developing lower-cost and higher-effective catalyst to support hydrogen(H_(2))production by electrochemical water-splitting has been recognized as a preferred strategy to drive the clean energy utilization.As a credible technology for the synthesis of functional materials,electrodeposition has attracted widespread attention,especially suitable for non-noble transition metal-based catalysts(TMCs).Recently,lots of researchers have been devoted to this hot research direction with plentiful achievements,however,a comprehensive review towards this area is still missing.Hence,we summarize the past research progress,presents the technical characteristics of electrodeposition from the viewpoint of fundamental theory and influence factors for the electrochemical deposition behavior,and introduce its application in various of TMCs with versatile nanostructures and compositions.Except a deeper and more comprehensive cognition of electrodeposition,we further discuss the catalyst’s optimized hydrogen evolution reaction(HER),oxygen evolution reaction(OER)performance as well as overall water splitting that combined with the synthetic process.Finally,we conclude the technical advantages towards electrodeposition,propose challenge and future research directions in this promising field.This timely review aims to promote a deeper understanding of effective catalysts obtained via electrodeposition strategy,and provide new guidance for the design and synthesis of future catalysts for hydrogen production.

Adsorption Mechanisms of Mesoporous Adsorbents in Solutions

Sieve effect, complexation, ionic exchange, electrostatic interaction, hydrogen bonding, hydrophobic interaction, and molecular recognition based on molecular imprinting are comprehensively discussed.

The latest development on amine functionalized solid adsorbents for post-combustion CO_(2)capture:Analysis review

Global warming and associated global climate change have led to serious efforts towards reducing CO_(2)emissions through the CO_(2)capture from the major emission sources.CO_(2)capture using the amine functionalized adsorbents is regard as a direct and effective way to reducing CO_(2)emissions due to their large CO_(2)adsorption amount,excellent CO_(2)adsorption selectivity and lower energy requirements for adsorbent regeneration.Moreover,large number of achievements on the amine functionalized solid adsorbent have been recorded for the enhanced CO_(2)capture in the past few years.In view of this,we review and analyze the recent advances in amine functionalized solid adsorbents prepared with different supporting materials including mesoporous silica,zeolite,porous carbon materials,metal organic frameworks(MOF)and other composite porous materials.In addition,amine functionalized solid adsorbents derived from waste resources are also reviewed because of the large number demand for cost-effective carbon dioxide adsorbents and the processing needs of waste resources.Considering the importance of the stability of the adsorbent in practical applications,advanced research in the capture cycle stability has also been summarized and analyzed.Finally,we summarize the review and offer the recommendations for the development of amine-based solid adsorbents for carbon dioxide capture.

Hydrogen Production via Hydrolysis and Alcoholysis of Light Metal-Based Materials:A Review

As an environmentally friendly and high-density energy carrier,hydrogen has been recognized as one of the ideal alternatives for fossil fuels.One of the major challenges faced by“hydrogen economy”is the development of efficient,low-cost,safe and selective hydrogen generation from chemical storage materials.In this review,we summarize the recent advances in hydrogen production via hydrolysis and alcoholysis of light-metal-based materials,such as borohydrides,Mg-based and Al-based materials,and the highly efficient regeneration of borohydrides.Unfortunately,most of these hydrolysable materials are still plagued by sluggish kinetics and low hydrogen yield.While a number of strategies including catalysis,alloying,solution modification,and ball milling have been developed to overcome these drawbacks,the high costs required for the“one-pass”utilization of hydrolysis/alcoholysis systems have ultimately made these techniques almost impossible for practical large-scale applications.Therefore,it is imperative to develop low-cost material systems based on abundant resources and effective recycling technologies of spent fuels for efficient transport,production and storage of hydrogen in a fuel cell-based hydrogen economy.