金属(氢)氧化物类除磷吸附剂研究进展

水体富营养是严重的环境问题,而控制水中的磷浓度对于缓解富营养化是至关重要的。金属(氢)氧化物具有优异的磷吸附特性,是理想的除磷材料。本文归纳了金属(氢)氧化物类吸附剂的除磷机理、影响因素以及常用的几类吸附剂。并结合不同的水处理场景,比选了不同物理化学性质的除磷吸附剂,指出设计材料时要平衡成本与除磷预期,不需要将吸附材料优化为除磷能力最高。并进一步提出吸附剂稳定性和安全性是未来研究值得考虑的问题。

金属(氢)氧化物对氟醚橡胶耐热老化性能的影响

考察了金属（氢）氧化物对氟醚橡胶耐热老化性能的影响，并从理论上进行了探讨。热重分析结果表明，在氟醚橡胶的热老化过程中没有明显的氧化裂解发生，但氧对其热老化有一定的促进作用；金属（氢）氧化物可以促进氟醚橡胶的硫化，并可使其生成热稳定性更高的交联结构，有利于提高氟醚橡胶的耐热老化性能。

金属(氢)氧化物参与木质素微生物转化形成类胡敏酸的结构特征分析

以木质素为碳源,并添加针铁矿、三羟铝石及δ-MnO 2,采用液体摇瓶培养法培养混合菌株,基于扫描电子显微镜(SEM)和固态13 C核磁共振波谱(CPMAS 13 C-NMR)对110 d培养期间矿物-菌体残留物提取的类胡敏酸(HLA)进行结构分析。结果表明,针铁矿、三羟铝石和δ-MnO 2参与木质素转化形成HLA的微观结构各不相同,形态分别为大小不一的片状、不规则且带有皱状边缘的球状以及表面凹凸不平、多褶皱的木耳状,由δ-MnO 2参与形成的HLA颗粒间有聚集趋势;与木质素相比,3种(氢)氧化物参与形成的HLA品质均有所改善,脂族化和亲水化程度加强;与国际腐殖质协会(IHSS)推荐的胡敏酸(HA)相比,针铁矿更易促进HLA的疏水化程度,增强木质素的保护机制,使脂族化程度相对稳定,而δ-MnO 2在提高HLA品质及亲水化程度方面更有优势;金属(氢)氧化物参与形成HLA的峰位及归属与秸秆还田土壤HA相似,但保留了木质素残余成分,部分芳香碳结构被O、N所取代,羧酸含量远低于IHSS推荐的HA。其中,由δ-MnO 2参与形成的HLA分子中出现了醌基,表明δ-MnO 2在促进木质素腐殖化作用方面优于针铁矿和三羟铝石,能够为腐殖质形成提供前体物质。

Adsorption of glutamic acid from aqueous solution with calcined layered double Mg-Fe-CO_3 hydroxide

Layered double Mg-Fe-CO3 hydroxide （Mg-Fe-LDH） with a mole ratio of Mg to Fe of 3 was synthesized by coprecipitation method and calcined product Mg-Fe-CLDH was obtained by heating Mg-Fe-LDH at 500 ℃ for 6 h. The as prepared Mg-Fe-LDH and calcined Mg-Fe-CLDH were used for removal of glutamic acid （Glu） from aqueous solution, respectively. Batch studies were carried out to address various experimental parameters such as contact time, pH, initial glutamic acid （Glu） concentration, co-existing anions and temperature. Glu was removed effectively （99.9%） under the optimized experimental conditions with Mg-Fe-CLDH. The adsorption kinetics follows the Ho’s pseudo second-order model. Isotherms for adsorption with Mg-Fe-CLDH at different solution temperatures were well described using the Langmuir model with a good correlation coefficient. The intraparticle diffusion model fitted the data well, which suggests that the intraparticle diffusion is not only the rate-limiting step.

A method for calculation of ion distribution in reaction system forming hydroxide

A formula was proposed to calculate the distribution of metal ions quantitatively in chemical reaction system forming hydroxide where precipitation and complex are formed together. The effects of some factors on formation of precipitation and complex were investigated, and the corresponding precipitation rates of zinc, iron （III）, aluminum, copper and magnesium were calculated. As a result, it shows that the proposed formula is reliable. By the proposed formula, the existence state of metal ions in hydroxides reaction system with any metal ions can be well described and the effects of some factors on the distribution of metal ions were determined.

STUDY ON DEGRADATION OF LDPE CATALYZED BY MULTI-VALENCE METALLIC ORGANIC COMPOUNDS AT COMPOST TEMPERATURE

The catalytic effects of the organic compounds of iron,tin and manganese on the degradation of low density polyethylene (LDPE) at compost temperature are discussed.A series of samples were aged in a simulating compost environment.The mechanical properties,viscosity average molecular weight (M η) of PE and hydroperoxide (POOH) concentration in the samples were measured.FT IR and DSC were also applied to characterize some samples.It was shown that the above mentioned metallic organic compounds can catalyze the degradation of LDPE efficiently.After 2 months aging,all samples with catalysts became fragile and the M η of the material decreased dramatically.Furthermore,the concentration of carbonyl and the degree of crystallinity of the material increased with the aging time.

Preparation and characterization of MWCNTs/LDHs nanohybrids for removal of Congo red from aqueous solution

The assembly of layered double hydroxides （LDHs） and multi-walled carbon nanotubes （MWCNTs） nanohybrids was prepared as MWCNTs/LDHs by co-precipitation. The synthesized nanoparticles were characterized by using XRD, FT-IR, SEM/EDX, TGA and BET. XRD and SEM studies proved that MWCNTs phases did not enter into the interlayers of LDHs, they dispersed over the LDHs surface homogeneously. BET results showed that MWCNTs/LDHs possessed hierarchically porous nanostructure with large surface area （124.974 m^2/g） and great pore volume （0.604 cm^3/g）. Batch experiments were conducted to study the adsorption efficiency of Congo red （CR）. It was worthy to note that MWCNTs/LDHs exhibited excellent adsorption performance with the maximum CR adsorption capacity of 595.8 mg/g in weak acidic environment. The adsorption kinetics and isotherm parameters can be well described by the pseudo-second-order and the Langmuir isotherm models, respectively. The thermodynamic studies indicated that the adsorption process was spontaneous and endothermic.

Enhanced corrosion resistance of micro-arc oxidation coated magnesium alloy by superhydrophobic Mg-Al layered double hydroxide coating

To further enhance the corrosion resistance of the porous micro-arc oxidation(MAO) ceramic layers on AZ31 magnesium alloy, superhydrophobic Mg-Al layered double hydroxide(LDH) coating was fabricated on MAO-coated AZ31 alloy by using in-situ growth method followed by surface modification with stearic acid. The characteristics of different coatings were investigated by XRD, SEM and EDS. The effect of the hydrothermal treatment time on the formation of the LDH coatings was studied. The results demonstrated that the micro-pores and cracks of MAO coating were gradually sealed via in-situ growing LDH with prolonging hydrothermal treating time. Electrochemical measurement displayed that the lowest corrosion current density, the most positive corrosion potential and the highest impedance modulus were observed for superhydrophobic LDH/MAO coating compared with those of MAO coating and LDH/MAO coating. Immersion experiment proved that the superhydrophobic LDH/MAO coating with the active anti-corrosion capability significantly enhanced the long-term corrosion protection for MAO coated alloy.

Selenium(Ⅵ) removal from caustic solution by synthetic Ca-Al-Cl layered double hydroxides

To extract selenium(Ⅵ)from the highly caustic leachate of copper anode slime,the Ca-Al-Cl layered double hydroxides(Ca-Al-Cl-LDHs)with a formula of Ca2 Al(OH)6 Cl·2 H2 O by three co-precipitation methods were synthesized.A plate-like morphology and hexagonal crystal structure with typical mineral phases and functional groups were identified by the FESEM,XRD,FTIR,BET and XPS analysis.The forward feeding sample exhibits the best adsorption capacity of Se(Ⅵ).The factor experiments then reveal a favorable adsorption process with low temperature,low NaOH concentration and high adsorbent dosage.Furthermore,the adsorption kinetics and isotherm parameters can be well described by the Langmuir isotherm and the pseudo-second-order models,respectively.Accordingly,the maximum adsorption amount of Se(Ⅵ)onto Ca-Al-Cl-LDHs reaches188.6 mg/g at 50 ℃.

2D materials modulating layered double hydroxides for electrocatalytic water splitting

Exploring highly efficient electrochemical water splitting catalysts has recently attracted extensive research interest from both fundamental researches and practical applications.Transition metal‐based layered double hydroxides(LDHs)have been proved to be one of the most efficient materials for oxygen evolution reaction(OER),however,still suffered from low conductivity and sluggish kinetics for hydrogen evolution reaction(HER),which largely inhibited the overall water splitting efficiency.To address this dilemma,enormous approaches including doping regulation,intercalation tuning and defect engineering are therefore rationally designed and developed.Herein,we focus on the recent exciting progress of LDHs hybridization with other two‐dimensional(2D)materials for water splitting reactions,not barely for enhancing OER efficiency but also for boosting HER activity.Particularly,the structural features,morphologies,charge transfer and synergistic effects for the heterostructure/heterointerface that influence the electrocatalytic performance are discussed in details.The hybrid 2D building blocks not only serve as additional conductivity and structural supported but also promote electron transfer at the interfaces and further enhance the electrocatalytic performance.The construction and application of the nanohybrid materials will guide a new direction in developing multifunctional materials based on LDHs,which will contribute to energy conversion and storage.

Layered double hydroxide photocatalysts for solar fuel production

Splitting water or reducing CO_(2) via semiconductor photocatalysis to produce H2 or hydrocarbon fuels through the direct utilization of solar energy is a promising approach to mitigating the current fossil fuel energy crisis and environmental challenges.It enables not only the realization of clean,renewable,and high-heating-value solar fuels,but also the reduction of CO_(2) emissions.Layered double hydroxides(LDHs)are a type of two-dimensional anionic clay with a brucite-like structure,and are characterized by a unique,delaminable,multidimensional,layered structure;tunable intralayer metal cations;and exchangeable interlayer guest anions.Therefore,it has been widely investigated in the fields of CO_(2) reduction,photoelectrocatalytic water oxidation,and water photolysis to produce H2.However,the low carrier mobility and poor quantum efficiency of pure LDH limit its application.An increasing number of scholars are exploring methods to obtain LDH-based photocatalysts with high energy conversion efficiency,such as assembling photoactive components into LDH laminates,designing multidimensional structures,or coupling different types of semiconductors to construct heterojunctions.This review first summarizes the main characteristics of LDH,i.e.,metal-cation tunability,intercalated guest-anion substitutability,thermal decomposability,memory effect,multidimensionality,and delaminability.Second,LDHs,LDH-based composites(metal sulfide-LDH composites,metal oxide-LDH composites,graphite phase carbon nitride-LDH composites),ternary LDH-based composites,and mixed-metal oxides for splitting water to produce H_(2) are reviewed.Third,graphite phase carbon nitride-LDH composites,MgAl-LDH composites,CuZn-LDH composites,and other semiconductor-LDH composites for CO_(2) reduction are introduced.Although the field of LDH-based photocatalysts has advanced considerably,the photocatalytic mechanism of LDHs has not been thoroughly elucidated;moreover,the photocatalytic active sites,the synergy between different components,and the interfacial reaction mechanism of LDH-based photocatalysts require further investigation.Therefore,LDH composite materials for photocatalysis could be developed through structural regulation and function-oriented design to investigate the effects of different components and interface reactions,the influence of photogenerated carriers,and the impact of material composition on the physical and chemical properties of the LDH-based photocatalyst.

Electronic structure regulation on layered double hydroxides for oxygen evolution reaction

Oxygen evolution reactions(OERs)as core components of energy conversion and storage technology systems,such as water splitting and rechargeable metal–air batteries,have attracted considerable attention in recent years.Transition metal compounds,particularly layered double hydroxides(LDHs),are considered as the most promising electrocatalysts owing to their unique two-dimensional layer structures and tunable components.However,heir poor intrinsic electrical conductivities and the limited number of active sites hinder their performances.The regulation of the electronic structure is an effective approach to improve the OER activity of LDHs,including cationic and anionic regulation,defect engineering,regulation of intercalated anions,and surface modifications.In this review,we summarize recent advances in the regulation of the electronic structures of LDHs used as electrocatalysts in OERs.In addition,we discuss the effects of each regulation type on OER activities.This review is expected to shed light on the development and design of effective OER electrocatalysts by summarizing various electronic structure regulation pathways and the effects on their catalytic performances.

Layered transition-metal hydroxides for alkaline hydrogen evolution reaction

Hydrogen is a promising sustainable energy to replace fossil fuels owning to its high specific energy and environmental friendliness.Alkaline water electrolysis has been considered as one of the most prospective technologies for large scale hydrogen production.To boost the sluggish kinetics of hydrogen evolution reaction(HER)in alkaline media,abundant materials have been designed and fabricated.Herein,we summarize the key achievements in the development of layered transition-metal hydroxides[TM(OH)x]for efficient alkaline HER.Based on the structure of TM(OH)x,the mechanism of synergistic effect between TM(OH)x and HER active materials is illuminated firstly.Then,recent progress of TM(OH)x-based HER catalysts to optimize the synergistic effect are categorized as TM(OH)x and active materials,including species,structure,morphology and interaction relationship.Furthermore,TM(OH)x-based overall water splitting electrocatalysts and electrodes are summarized in the design principles for high activity and stability.Finally,some of key challenges for further developments and applications of hydrogen production are proposed.

Fabrication of cobalt aluminum-layered double hydroxide nanosheets/carbon spheres composite as novel electrode material for supercapacitors

A new design route was presented to fabricate cobalt aluminum-layered double hydroxide(CoAl-LDH)thin layers whichgrow on carbon spheres(CSs)through a growth method.The CoAl-LDH thin layers consist of nanoflakes with a thickness of20nm.The galvanostatic charge-discharge test of the CoAl-LDH/CSs composite shows a great specific capacitance of1198F/g at1A/g(based on the mass of the CoAl-LDH/CSs composite)in6mol/L KOH solution,and the composite displays an impressive specificcapacitance of920F/g even at a high current density of10A/g.Moreover,the composite remains a specific capacitance of928F/gafter1000cycles at2A/g,and the specific capacitance retention is84%,indicating that the composite has high specific capacitance,excellent rate capability and good cycling stability in comparison to pristine CoAl-LDH.

Self-supporting NiFe LDH-MoS_(x) integrated electrode for highly efficient water splitting at the industrial electrolysis conditions

Developing effective and practical electrocatalyst under industrial electrolysis conditions is critical for renewable hydrogen production.Herein,we report the self-supporting NiFe LDH-MoS_(x) integrated electrode for water oxidation under normal alkaline test condition(1 M KOH at 25℃)and simulated industrial electrolysis conditions(5 M KOH at 65℃).Such optimized electrode exhibits excellent oxygen evolution reaction(OER)performance with overpotential of 195 and 290 mV at current density of 100 and 400 mA·cm^(-2) under normal alkaline test condition.Notably,only over-potential of 156 and 201 mV were required to achieve the current density of 100 and 400mA·cm^(-2) under simulated industrial electrolysis conditions.No significant degradations were observed after long-term durability tests for both conditions.When using in two-electrode system,the operational voltages of 1.44 and 1.72 V were required to achieve a current density of 10 and 100 mA·cm^(-2) for the overall water splitting test(NiFe LDH-MoS_(x)/INF||20%Pt/C).Additionally,the operational voltage of employing NiFe LDH-MoS_(x)/INF as both cathode and anode merely require 1.52 V at 50mA·cm^(-2) at simulated industrial electrolysis conditions.Notably,a membrane electrode assembly(MEA)for anion exchange membrane water electrolysis(AEMWEs)using NiFe LDH-MoS_(x)/INF as an anode catalyst exhibited an energy conversion efficiency of 71.8%at current density of 400 mA·cm^(-2)in 1 M KOH at 60℃.Further experimental results reveal that sulfurized substrate not only improved the conductivity of NiFe LDH,but also regulated its electronic configurations and atomic composition,leading to the excellent activity.The easy-obtained and cost-effective integrated electrodes are expected to meet the large-scale application of industrial water electrolysis.

Intercalation Assembly Method and Intercalation Process Control of Layered Intercalated Functional Materials

Layered intercalated functional materials of layered double hydroxide type are an important class of functional materials developed in recent years. Based on long term studies on these materials in the State Key Laboratory of Chemical Resource Engineering in Beiiing University of Chemical Technology, the orinciole for the design of controlled intercalation processes in the light of tuture production processing requirements has been developed. Intercalation assembly methods and technologies have been invented to control the intercalation process for preparing layered intercalated materials with various structures and functions.

Influence of Synthesis Temperature on Phosphate Adsorption by Zn-Al Layered Double Hydroxides in Excess Sludge Liquor

A group of Zn-Al layered double hydroxides (LDHs) were synthesized at different temperatures from 25-90 °C in order to investigate the influence of synthesis temperature on characteristics of the LDHs and their phosphate adsorption behaviour. The results reveal that an increase in the synthesis temperature generally improves the specific surface area of the sample and the phosphate adsorption capacity. The significantly enhanced crystallin- ity of the Zn-Al-30, synthesized at 30 °C, leads to a remarkable decrease in the specific surface area and consequently a poor phosphate adsorption capacity. It is suggested that the surface adsorption plays an important role in the phosphate uptake by the Zn-Al LDHs. Zn-Al-70 presents a relatively higher crystallinity and a lower specific surface area, compared with Zn-Al-60 and Zn-Al-80, but the highest phosphate adsorption capacity, indicating that surface adsorption is only one of the pathways for phosphate removal. The phosphate adsorption by the Zn-Al follows a pseudo-second-order kinetic equation. The adsorption isotherms fit Langmuir models, and the maximum a dsorption capacities of the Zn-Al-25, Zn-Al-50 and Zn-Al-70 are estimated to be 17.82, 21.01 and 27.10 mg·g-1 adsorbent, respectively.

In situ formation of amorphous Fe-based bimetallic hydroxides from metal-organic frameworks as efficient oxygen evolution catalysts

Oxygen evolution from water driven by electrocatalysis or photocatalysis poses a significant challenge as it requires the use of efficient electro-/photo-catalysts to drive the four-electron oxygen evolution reaction(OER).Herein,we report the development of an effective strategy for the in situ chemical transformation of Fe-based bimetallic MIL-88 metal-organic frameworks(MOFs)into corresponding bimetallic hydroxides,which are composed of amorphous ultrasmall nanoparticles and afford an abundance of catalytically active sites.Optimized MOF-derived NiFe-OH-0.75 catalyst coated on glassy carbon electrodes achieved a current density of 10 mA cm^(-2)in the electrocatalytic OER with a small overpotential of 270 mV,which could be decreased to 235 mV when loading the catalysts on a nickel foam substrate.Moreover,these MOF-derived Fe-based bimetallic hydroxides can be used as efficient cocatalysts when combined with suitable photosensitizers for photocatalytic water oxidation.

Electrochemically formed PtFeNi alloy nanoparticles on defective NiFe LDHs with charge transfer for efficient water splitting

Efficient and stable bifunctional electrocatalysts for water splitting is essential for producing hydrogen and alleviating huge energy consumption.Meanwhile,charge transfer engineering is an efficient approach to modulate the localized electronic properties of catalysts and tune the electrocatalytic performance.Herein,we tactfully fabricate PtFeNi alloys/NiFe layered double hydroxides(LDHs)heterostructure by an easily electrochemical way with a small amount of Pt.The experimental and theoretical results unravel that the charge transfer on the alloy clusters modulated by the defective substrates(NiFe LDHs),which synergistically optimizes the adsorption energy of the reaction intermediates.The electrocatalyst exhibits an ultra‐low overpotential of 81 and 243 mV at the current density of 100 mA cm^(–2) for hydrogen evolution and oxygen evolution,respectively.Furthermore,the overall water splitting indicates that PtFeNi alloys/NiFe LDHs presents an ultra‐low overpotential of 265 and 406 mV to reach the current density of 10 and 300 mA cm^(–2),respectively.It proves that the PtFeNi alloys/NiFe LDHs catalyst is an excellent dual‐function electrocatalyst for water splitting and promising for industrialization.This work provides a new electrochemical approach to construct the alloy heterostructure.The prepared heterostructures act as an ideal platform to investigate the charge re‐distribution behavior and to improve the electrocatalytic activity.

Practice and design of the self-purification system for heavy metals-bearing contaminants

Many minerals in nature have self-purification capacity to hold and stabilize deleterious contaminants into their lattice structures,which can be used for treatment of heavy metals-bearing contaminants. Hydrotalcite Layer Double Hydroxide (LDH),tobermorite Calcium Silicate Hydrate (CSH) and apatite are ubiquitous minerals in nature,having higher geochemical stability and potential for binding and stabilizing heavy metals. Based on the elucidation of crystal structure property and self-purification principles of the three minerals above,this article discussed how to design the self-purification system of heavy metal-bearing contaminants.