Solid amine sorbents for CO_(2) capture by chemical adsorption: A review

Amines are well-known for their reversible reactions with CO_(2),which make them ideal for CO_(2) capture from several gas streams,including flue gas.In this respect,selective CO_(2) absorption by aqueous alkanolamines is the most mature technology but the process is energy intensive and has also corrosion problems.Both disadvantages can be diminished to a certain extent by chemical adsorption of CO_(2) selectively.The most important element of the chemical adsorption of CO_(2) involves the design and development of a suitable adsorbent which consist of a porous support onto which an amine is attached or immobilized.Such an adsorbent is often called as solid amine sorbent.This review covers solid amine-based studies which are developed and published in recent years.First,the review examines several different types of porous support materials,namely,three mesoporous silica(MCM-41,SBA-15 and KIT-6)and two polymeric supports(PMMA and PS)for CO_(2) adsorption.Emphasis is given to the synthesis,modifications and characterizations-such as BET and PXRD data-of them.Amination of these supports to obtain a solid amine sorbent through impregnation or grafting is reviewed comparatively.Focus is given to the adsorption mechanisms,material characteristics,and synthesis methods which are discussed in detail.Significant amount of original data are also presented which makes this review unique.Finally,relevant CO_(2) adsorption(or equilibrium)capacity data,and cyclic adsorption/desorption performance and stability of important classes of solid amine sorbents are critically reviewed.These include severa PEI or TEPA impregnated adsorbents and APTES-grafted systems.

Thermodynamics, kinetics and mechanism analysis of Cu(Ⅱ) adsorption by in-situ synthesized struvite crystal

Synthesized struvite was innovatively applied to removing Cu（II） from aqueous solution. The Cu（II） adsorption behavior and relative mechanisms were studied and analyzed. The maximum Cu（II） adsorption under pH=4.0 and 318 K calculated from adsorption thermodynamic analysis was 145.1 mg/g. The sorption kinetics can be favorably described by pseudo-second order model. The activation energy （Ea） of 17.5 kJ/mol suggested that the adsorption process was a chemical adsorption. The calculated thermodynamic parameters indicated that the adsorption was a spontaneous and endothermic one. On the basis of characterization upon struvite before and after adsorption, it was found that the electrostatic attraction and coordination bonding supported the ion sorption on struvite surface, and the transformation of copper ion into copper hydroxide occurred on struvite surface and within its crevices.

ADSORPTION OF 2,4-DICHLOROBENZOXYACETIC ACID ONTO HYPERCROSSLINKED RESIN MODIFIED BY PHENOLIC HYDROXYL GROUP (AM-1)

An experimental comparison of the adsorption properties of hypercrosslinked resin AM-1 modified by phenolic hydroxyl group with Amberlite XAD-4 toward 2,4-dichlorobenzoxyacetic acid was performed. This paper focuses on the static equilibrium adsorption behaviors and the adsorption thermodynamics. Two isotherm models were used to explain the results. It is seen that the Langmuir equation can give a perfect fit. The adsorption capacities from the different ranges of temperature, the adsorption enthalpy change value and the comparison of desorption conditions lead to the same conclusion that the adsorption of 2,4-dichlorobenzoxyacetic acid from water onto AM-1 is a type of physical and chemical transition.

Structure of Reconstructed Cu（100） Surface Induced by Dissociative Adsorption of Gaseous Oxygen

The reconstructed structures of Cu（100） surface induced by O2 dissociative adsorption were investigated by low energy electron diffraction and scanning tunneling microscopy. At lower oxygen coverage, it was found that two reconstructed structures, i.e. c（2×2）-O and （√2×2√2）R45°-O are coexistent. The domain size of the c（2×2）-O structure decreased with the increasing of O2 exposure. The reconstructed structure at very small coverage was also investigated and a “zigzag” structure was observed at this stage. The “zigzag” structure was identified as boundaries of local c（2×2） domains. It was found that the strip region shows much stronger molecule-substrate interaction than that of oxygen covered regions, making it a proper template for patterned organic films. The sequence of the thermal stability was found as zigzag structure〉c（2×2）〉（√2×2√2）R45°-O.

Revisiting the Role of Physical Confinement and Chemical Regulation of 3D Hosts for Dendrite-Free Li Metal Anode

Lithium metal anode has been demonstrated as the most promising anode for lithium batteries because of its high theoretical capacity,but infinite volume change and dendritic growth during Li electrodeposition have prevented its practical applications.Both physical morphology confinement and chemical adsorption/diffusion regulation are two crucial approaches to designing lithiophilic materials to alleviate dendrite of Li metal anode.However,their roles in suppressing dendrite growth for long-life Li anode are not fully understood yet.Herein,three different Ni-based nanosheet arrays(NiO-NS,Ni_(3)N-NS,and Ni_(5)P_(4)-NS)on carbon cloth as proof-of-concept lithiophilic frame-works are proposed for Li metal anodes.The two-dimensional nanoarray is more promising to facilitate uniform Li^(+)flow and electric field.Compared with the NiO-NS and the Ni_(5)P_(4)-NS,the Ni_(3)N-NS on carbon cloth after reacting with molten Li(Li-Ni/Li_(3)N-NS@CC)can afford the strongest adsorption to Li+and the most rapid Li+diffusion path.Therefore,the Li-Ni/Li_(3)N-NS@CC electrode realizes the lowest overpotential and the most excellent electrochemical performance(60 mA cm^(−2)and 60 mAh cm^(−2)for 1000 h).Furthermore,a remarkable full battery(LiFePO_(4)||Li-Ni/Li_(3)N-NS@CC)reaches 300 cycles at 2C.This research provides valuable insight into designing dendrite-free alkali metal batteries.

Fabrication and characterization of Fe_3O_4@SiO_2@TiO_2@Ho nanostructures as a novel and highly efficient photocatalyst for degradation of organic pollution

In this work we synthesize a novel and highly efficient photocatalyst for degradation of methyl orange and rhodamine B. In addition, a new method for synthesis of FeO@SiO@TiO@Ho magnetic core-shell nanoparticles with spherical morphology is proposed. The crystal structures, morphology and chemical properties of the as-synthesized nanoparticles were characterized using Fourier transform infrared spectroscopy（FT-IR）, scanning electron microscopy（SEM）, transmission electron microscopy（TEM）, energy dispersive X-ray（EDS）, X-ray diffraction（XRD）, UV–vis diffuse reflectance spectroscopy（DRS） and vibrating sample magnetometer（VSM） techniques. The photocatalytic activity of FeO@SiO@TiO@Ho was investigated by degradation of methyl orange（MO） as cationic dye and rhodamine B（Rh B） as anionic dye in aqueous solution under UV/vis irradiation. The results indicate that about 92.1% of Rh B and78.4% of MO were degraded after 120 and 150 min, respectively. These degradation results show that FeO@SiO@TiO@Ho nanoparticles are better photocatalyst than Fe3O4@Si O2@TiO 2@Ho for degradation of MO and Rh B. As well as, the catalyst shows high recovery and stability even after several separation cycles.

High-performance lithium-sulfur battery based on porous N-rich g-C_(3)N_(4) nan-otubes via a self-template method

The commercial development of lithium-sulfur batteries(Li-S)is severely limited by the shuttle effect of lithium polysulfides(LPSs)and the non-conductivity of sulfur.Herein,porous g-C_(3)N_(4) nanotubes(PCNNTs)are synthesized via a self-template method and utilized as an efficient sulfur host material.The one-dimensional PCNNTs have a high specific surface area(143.47 m^(2)·g^(-1))and an abundance of macro-/mesopores,which could achieve a high sulfur loading rate of 74.7wt%.A Li-S battery bearing the PCNNTs/S composite as a cathode displays a low capacity decay of 0.021% per cycle over 800 cycles at 0.5 C with an initial capacity of 704.8 mAh·g^(-1).PCNNTs with a tubular structure could alleviate the volume expansion caused by sulfur and lithium sulfide during charge/discharge cycling.High N contents could greatly enhance the adsorption capacity of the carbon nitride for LPSs.These synergistic effects contribute to the excellent cycling stability and rate performance of the PCNNTs/S composite electrode.

Removal of aqueous Ni(Ⅱ) with carbonized leaf powder: Kinetics and equilibrium

Nickel is a heavy metal which has the potential threaten to human＇s health and attracts public concern recently. The carbonized leaf powder is expected as suitable adsorbent for Ni（II） removal became of the composition of some beneficial groups. In this work, carbonized leaf powder was evaluated for its adsorption performance towards Ni（II）. According to the results, adsorbent component, dosage, initial solute concentration, solution pH, temperature and contact time can significantly affect the efficiency of Ni（II） removal. Sips model fits the test results best, and the adsorption capacity towards Ni（II） is determined around 37.62 mg/g. The thermodynamic behaviors reveal the endothermic and spontaneous nature of the adsorption. The free adsorption energy （fluctuate around 8 kJ/mol） predicted by D-R model indicates that the adsorption capacity originated from both physical and chemical adsorption. Room temperature （15-25 ℃） is suitable for Ni（II） removal as well as low energy consumption for temperature enhancement. Further conclusions about the mechanism of chemical adsorption are obtained through analysis of the FT-IR test and XRD spectra, which indicates that the adsorption process occurs predominantly between amine, carbonate, phosphate and nickel ions.

Monodisperse polar NiCo_(2)O_(4) nanoparticles decorated porous graphene aerogel for high-performance lithium sulfur battery

Lithium sulfur battery(LSB)is a promising energy storage system to meet the increasing energy demands for electric vehicles and smart grid,while its wide commercialization is severely inhibited by the"shuttle effect"of polysulfides,low utilization of sulfur cathode,and safety of lithium anode.To overcome these issues,herein,monodisperse polar NiCo_(2)O_(4)nanoparticles decorated porous graphene aerogel composite(NCO-GA)is proposed.The aerogel composite demonstrates high conductivity,hierarchical porous structure,high chemisorption capacity and excellent electrocatalytic ability,which effectively inhibits the"shuttle effect",promotes the ion/electron transport and increases the reaction kinetics.The NCO-GA/S cathode exhibits high discharge specific capacity(1214.1 mAh g^(-1)at 0.1 C),outstanding rate capability(435.7 mAh g^(-1)at 5 C)and remarkable cycle stability(decay of 0.031%/cycle over 1000 cycles).Quantitative analyses show that the physical adsorption provided by GA mainly contributes to the capacity of NCO-GA/S at low rate,while the chemical adsorption provided by polar NiCo_(2)O_(4)contributes mainly to the capacity of NCO-GA/S with the increase of current density and cycling.This work provides a new strategy for the design of GA-based composite with synergistic adsorption and electrocatalytic activity for the potential applications in LSB and related energy fields.

Poly(thiourea triethylene glycol) as a multifunctional binder for enhanced performance in lithium-sulfur batteries

A mechanically strong binder with polar functional groups could overcome the dilemma of the large volume change during charge/discharge processes and poor cyclability of lithium-sulfur batteries(LSBs).In this work,for the first time,we report the use of poly(thiourea triethylene glycol)(PTTG)as a multifunctional binder for sulfur cathodes to enhance the performance of LSBs.As expected,the PTTG binder facilitates the high performance and stability delivered by the Sulfur-PTTG cathode,including a higher reversible capacity of 825 mAh g^(-1) at 0.2 C after 80 cycles,a lower capacity fading(0.123%per cycle)over 350 cycles at 0.5 C,a higher areal capacity of 2.5 mAh cm^(-2) at 0.25 mA cm^(-2),and better rate capability of 587 mAh g^(-1) at 2 C.Such superior electrochemical performances could be attributed to PTTG's strong chemical adsorption towards polysulfides which may avoid the lithium polysulfide shuttle effect and excellent mechanical characteristics which prevents electrode collapse during cycling and allows the Sulfur-PTTG electrode to maintain robust electron and ion migration pathways for accelerated redox reaction kinetics.

Catalytic Performance and IR Characterization of Co-Mo/Al_2O_3 and Ru-Co-Mo/Al_2O_3 Catalysts in Hydrodesulfurization

Recently, owing to high costs and increasing demands for better catalysts, it is worthwhile to improve its activity and selectivity, and reduce its costs. Adding secondary promoters such as phosphorus, boron, magnesium, titanium, zinc and ruthenium to Co-Mo/Al;O;catalyst has been proved to be one of the ways to attain this result. The addition of those metals or metal oxides changes the surface states of molybdenumstructure.

Crude Extract of Detergent⁃Like Gleditsia sinensis lam Exhibiting Self⁃Organization for Protection of Mild Steel in Harsh Hydrochloric Acid Solution:How to Seek Crude Natural Plant Extracts as Green Corrosion Inhibitors

This study proposes a thought to employ detergent⁃like renewable low⁃cost crude extract of Gleditsia sinensis lam(GSL)as green corrosion inhibitor for mild steel in HCl solution.Crude Gleditsia sinensis lam extract(GSLE)was gained at mild conditions by simply refluxing in ethanol with a Soxhlet extractor.The target GSLE extract exhibited regular self⁃organization in mixed solvents of organic solvents/H2O such as ethanol/H2 O(v/v,50/50)at room temperature,which was evidenced by different means including scanning electron microscopy,transmission electron microscopy,and dynamic light scattering.The study demonstrates that the yielded assemblies of the crude extract of GSLE displayed chemical adsorption on the studied mild steel sample surfaces.Furthermore,the formed stable crude extract assemblies of GSL presented outstanding anti⁃corrosion capability in 1.0 mol/L HCl aqueous solution based on electrochemical measurements including polarization curves and impedance spectroscopy.It is discovered that the maximal corrosion inhibition efficiency could reach approximate 95%.The molecular modeling was performed to acquire the nature of frontier orbitals of the main representative chemical components of crude GSLE for deep understanding of chemical interactions with iron.The results presented herein would guide us to seek sustainable environmentally friendly low⁃cost detergent⁃like plant crude extracts for corrosion inhibition of various metals in aggressive acid environments.

Adsorption and biodegradation of three selected endocrine disrupting chemicals in river-based artificial groundwater recharge with reclaimed municipal wastewater

Endocrine disrupting chemical（EDC） pollution in river-based artificial groundwater recharge using reclaimed municipal wastewater poses a potential threat to groundwater-based drinking water supplies in Beijing, China. Lab-scale leaching column experiments simulating recharge were conducted to study the adsorption, biodegradation, and transport characteristics of three selected EDCs： 17β-estradiol（E2）, 17α-ethinylestradiol（EE2） and bisphenol A（BPA）. The three recharge columns were operated under the conditions of continual sterilization recharge（CSR）, continual recharge（CR）, and wetting and drying alternative recharge（WDAR）. The results showed that the attenuation effect of the EDCs was in the order of WDAR 〉 CR 〉 CSR system and E2 〉 EE2 〉 BPA, which followed first-order kinetics. The EDC attenuation rate constants were 0.0783, 0.0505, and 0.0479 m-1 for E2, EE2 and BPA in the CR system, respectively. The removal rates of E2, EE2, and BPA in the CR system were 98%, 96% and 92%, which mainly depended on biodegradation and were affected by water temperature.In the CR system, the concentrations of BPA, EE2, and E2 in soil were 4, 6 and 10 times higher than in the WDAR system, respectively. According to the DGGE fingerprints, the bacterial community in the bottom layer was more diverse than in the upper layer, which was related to the EDC concentrations in the water-soil system. The dominant group was found to be proteobacteria, including Betaproteobacteria and Alphaproteobacteria, suggesting that these microbes might play an important role in EDC degradation.

Preparation of TiO2 Nanocrystals/Graphene Composite and Its Photocatalytic Performance

TiO2 nanocrystals/graphene （TiO2/GR） composite are prepared by combining flocculation and hydrothermal reduction technology using graphite oxide and TiO2 colloid as precursors. The obtained materials are examined by scanning electron microscopy, transition electron microscopy, X-ray diffraction, N2 adsorption desorption, and ultraviolet-visible diffuse spectroscopy. The results suggest that the presence of TiO2 nanocrystals with diameter of about 15 nm prevents GR nanosheets from agglomeration. Owing to the uniform distribution of TiO2 nanocrystals on the GR nanosheets, TiO2/GR composite exhibits stronger light absorption in the visible region, higher adsorption capacity to methylene blue and higher efficiency of charge separation and transportation compared with pure TiO2. Moreover, the TiO2/GR composite with a GR content of 30% shows higher photocatalytic removal efficiency of MB from water than that of pure TiO2 and commercial P25 under both UV and sunlight irradiation.

Templated spherical coassembly strategy to fabricate MoS_(2)/C hollow spheres with physical/chemical polysulfides trapping for lithium-sulfur batteries

Rational design of advanced polar hosts with high sulfur loading,facilitated ionic/electronic transport and effectively suppressed shuttling effect has great potential for high performance lithium-sulfur batteries,yet it remains challenging.Here we propose a novel templated spherical coassembly strategy to fabricate the MoS_(2)/C hollow spheres as an efficient sulfur host material.The unique hollow structure provides enough interior space for accommodating a substantial amount of sulfur,and effectively suppresses the diffusion of dissolved polysulfides by both physical confinement and chemical adsorption.Moreover,the ionic transport as well as the ability to mitigate volume variation upon cycling is also improved,thereby maximizing the utilization of sulfur.Owing to these merits,when evaluated as a sulfur host for lithiumsulfur batteries,the MoS_(2)/C hollow spheres exhibit appealing electrochemical performance with an impressive specific capacity of 1082 mA hg^(-1)at 0.1 C,excellent rate capability and superior cycling stability with a low fading rate of 0.04%per cycle.

Theoretical study of ZnO adsorption and bonding on Al_2O_3(0001) surface

ZnO adsorption on sapphire (0001) surface is theoretically calculated by using a plane wave ultrasoft pseudo-potential method based on ab initio molecular dynamics. The results reveal that the surface relaxation in the first layer Al-O is reduced, even eliminated after the surface adsorption of ZnO, and the chemical bonding energy is 434.3(±38.6) kJ·mol?1. The chemical bond of ZnO (0.185 ± 0.01 nm) has a 30° angle away from the adjacent Al-O bond, and the stable chemical adsorption position of the Zn is deflected from the surface O-hexagonal symmetry with an angle of about 30°. The analysis of the atomic populations, density of state and bonding electronic density before and after the adsorption indicates that the chemical bond formed by the O2 of the ZnO ? and the surface Al3+ has a strong ionic bonding characteristic, while the chemical bond formed by the Zn2+ and the surface O2 has an obvious covalent characteristic, which ? comes mainly from the hybridization of the Zn 4s and the O 2p and partially from that of the Zn 3d and the O 2p.

Titanium nitride nanorod array/carbon cloth as flexible integrated host for highly stable lithium-sulfur batteries

Lithium-sulfur(Li-S)batteries have been regarded as promising energy-storage systems,due to their high theoretical capacity and energy density.However,the carbonaceous sulfur hosts suffer from weak binding force between the hosts and polysulfides,restricting the cyclic stability of sulfur electrode.Meantime,the presence of binder and conductive agent in the traditional electrode reduces its energy density.This study demonstrates that titanium nitride(TiN)nanorod array on carbon cloth(CC)is employed as a flexible host for highly stable Li-S batteries via solvothermal synthesis-nitridation strategy.On the one hand,the flexible integrated network composed of three-dimensional TiN nanorod array and CC significantly improves the conductivity,increases the electron transport and electrolyte penetration of cathode.On the other hand,the 3D structure of TiN/CC and the enhanced polarity of TiN effectively strengthen the physical and chemical double adsorption for polysulfides.As a result,the combination of TiN nanorod array and CC synergistic ally promotes sulfur utilization and electrochemical performances of S@TiN/CC cathode.A discharge capacity of1015.2 mAh·g^(-1)at 0.5C after 250 cycles and 604.1mAh·g^(-1)at 3C after 250 cycles is realized.Under a larger current density of 5C,the resulting S@TiN/CC cathode maintains a high discharge capacity of 666.6 mAh·g^(-1)and the Coulombic efficiency of about 100%.

High-yield red phosphorus sponge mediated robust lithium-sulfur battery

Although lithium-sulfur(Li-S)batteries with high specific energy exhibit great potential for next-generation energy-storage systems,their practical applications are limited by the growth of Li dendrites and lithium polysulfides(LiPSs)shuttling.Herein,a highly porous red phosphorus sponge(HPPS)with well distributed pore structure was efficiently prepared via a facile and largescale hydrothermal process for polysulfides adsorption and dendrite suppression.As experimental demonstrated,the porous red phosphorus modified separator with increased active site greatly promotes the chemisorption of LiPSs to efficiently immobilize the active sulfur within the cathode section,while Li metal anode activated by Li_(3)P interlayer with abundant ionically conductive channels significantly eliminates the barrier for uniform Li^(+)permeation across the interlayer,contributing to the enhanced stability for both S cathode and Li anode.Mediated by the HPPS,long-term stability of 1,200 h with minor voltage hysteresis is achieved in symmetric cells with Li_(3)P@Li electrode while Li-S half-cell based on HPPS modified separator delivers an outperformed reversibility of 783.0 mAh·g^(−1)after 300 cycles as well as high-rate performance of 694.5 mAh·g^(−1)at 3 C,which further boosts the HPPS tuned full cells in practical S loading(3 mg·cm^(−2))and thin Li3P@Li electrode(100μm)with a capacity retention of 71.8%after 200 cycles at 0.5 C.This work provides a cost-effective and metal free mediator for simultaneously alleviating the fundamental issues of both S cathode and Li anode towards high energy density and long cycle life Li-S full batteries.

Specific ion effect of H^(+) on variably charged soil colloid aggregation

Specific ion effects(Hofmeister effects)have recently attracted the attention of soil scientists,and it has been found that ionic non-classic polarization plays an important role in the specific ion effect in soil.However,this explanation cannot be applied to H+.The aim of this work was to characterize the specific ion effect of H+on variably charged soil(yellow soil)colloid aggregation.The total average aggregation(TAA)rate,critical coagulation concentration(CCC),activation energy,and zeta potential were used to characterize and compare the specific ion effects of H+,K+,and Na+.Results showed that strong specific ion effects of H+,K+,and Na+existed in variably charged soil colloid aggregation.The TAA rate,CCC,and activation energy were sensitive to H+,and the addition of a small amount of H+changed the TAA rate,CCC,and activation energy markedly.The zeta potential results indicated that the specific ion effects of H+,K+,and Na+on soil colloid aggregation were caused by the specific ion effects of H+,K+,and Na+on the soil electric field strength.In addition,the origin of the specific ion effect for H+was its chemical adsorption onto surfaces,while those for alkali cations were non-classic polarization.This study indicated that H+,which occurs naturally in variably charged soils,will dominate variably charged soil colloid aggregation.

Experimental and theoretical studies on the removal mechanism of formaldehyde from water by mesoporous calcium silicate

Most porous materials with high specific surface area and diverse internal structures possess good adsorption ability.In this work,a tremella-like mesoporous calcium silicate hydrate(CSH)with high adsorption capacity was successfully prepared via a facile hydrothermal method.The adsorption effect and adsorption mechanism of the as-prepared calcium silicate hydrate(APCSH)towards formaldehyde from water were investigated systematically.Results indicate that AP-CSH has high Ca/Si ratio(1.95),large specific surface area(122.83 m2 g-1)and exhibits excellent adsorption capacity.The results of batch adsorption experiments show that AP-CSH can remove formaldehyde from water rapidly and effectively with the maximum removal efficiency of 98.94%.The adsorption process agrees well with the pseudo-second-order and Freundlich isotherm model.Furthermore,regeneration can be achieved by simply immersing AP-CSH in absolute ethanol and the removal efficiency can still reach about 99.50%after five cycles.The adsorption mechanism was also studied by experimental analyses and molecular dynamics simulation.Both experimental results and theoretical simulation support that formaldehyde adsorption over AP-CSH belongs to chemical adsorption.