Enabling heterogeneous catalysis to achieve carbon neutrality: Directional catalytic conversion of CO_(2) into carboxylic acids

The increase in anthropogenic carbon dioxide(CO_(2))emissions has exacerbated the deterioration of the global environment,which should be controlled to achieve carbon neutrality.Central to the core goal of achieving carbon neutrality is the utilization of CO_(2) under economic and sustainable conditions.Recently,the strong need for carbon neutrality has led to a proliferation of studies on the direct conversion of CO_(2) into carboxylic acids,which can effectively alleviate CO_(2) emissions and create high-value chemicals.The purpose of this review is to present the application prospects of carboxylic acids and the basic principles of CO_(2) conversion into carboxylic acids through photo-,electric-,and thermal catalysis.Special attention is focused on the regulation strategy of the activity of abundant catalysts at the molecular level,inspiring the preparation of high-performance catalysts.In addition,theoretical calculations,advanced technologies,and numerous typical examples are introduced to elaborate on the corresponding process and influencing factors of catalytic activity.Finally,challenges and prospects are provided for the future development of this field.It is hoped that this review will contribute to a deeper understanding of the conversion of CO_(2) into carboxylic acids and inspire more innovative breakthroughs.

Mitigating Lattice Distortion of High‑Voltage LiCoO_(2)via Core‑Shell Structure Induced by Cationic Heterogeneous Co‑Doping for Lithium‑Ion Batteries

Inactive elemental doping is commonly used to improve the structural stability of high-voltage layered transition-metal oxide cathodes.However,the one-step co-doping strategy usually results in small grain size since the low diffusivity ions such as Ti^(4+)will be concentrated on grain boundaries,which hinders the grain growth.In order to synthesize large single-crystal layered oxide cathodes,considering the different diffusivities of different dopant ions,we propose a simple two-step multi-element co-doping strategy to fabricate core–shell structured LiCoO_(2)(CS-LCO).In the current work,the high-diffusivity Al^(3+)/Mg^(2+)ions occupy the core of single-crystal grain while the low diffusivity Ti^(4+)ions enrich the shell layer.The Ti^(4+)-enriched shell layer(~12 nm)with Co/Ti substitution and stronger Ti–O bond gives rise to less oxygen ligand holes.In-situ XRD demonstrates the constrained contraction of c-axis lattice parameter and mitigated structural distortion.Under a high upper cut-off voltage of 4.6 V,the single-crystal CS-LCO maintains a reversible capacity of 159.8 mAh g^(−1)with a good retention of~89%after 300 cycles,and reaches a high specific capacity of 163.8 mAh g^(−1)at 5C.The proposed strategy can be extended to other pairs of low-(Zr^(4+),Ta^(5+),and W6+,etc.)and high-diffusivity cations(Zn^(2+),Ni^(2+),and Fe^(3+),etc.)for rational design of advanced layered oxide core–shell structured cathodes for lithium-ion batteries.

Outage Probability Analysis for D2D-Enabled Heterogeneous Cellular Networks with Exclusion Zone:A Stochastic Geometry Approach

Interference management is one of the most important issues in the device-to-device(D2D)-enabled heterogeneous cellular networks(HetCNets)due to the coexistence of massive cellular and D2D devices in which D2D devices reuse the cellular spectrum.To alleviate the interference,an efficient interference management way is to set exclusion zones around the cellular receivers.In this paper,we adopt a stochastic geometry approach to analyze the outage probabilities of cellular and D2D users in the D2D-enabled HetCNets.The main difficulties contain three aspects:1)how to model the location randomness of base stations,cellular and D2D users in practical networks;2)how to capture the randomness and interrelation of cellular and D2D transmissions due to the existence of random exclusion zones;3)how to characterize the different types of interference and their impacts on the outage probabilities of cellular and D2D users.We then run extensive Monte-Carlo simulations which manifest that our theoretical model is very accurate.

Fe_3O_4@UiO-66-NH_2 core–shell nanohybrid as stable heterogeneous catalyst for Knoevenagel condensation

separation is an attractive alternative to filtration or centrifugation for separating solid catalysts from a liquid phase, Here, core-shell Fe3O4@UiO-66-NH2 nanohybrids with well-defined structures were constructed by dispersing magnets in a dimethylformamide （DMF） solution con- taining two metal-organic framework （MOF） precursors, namely ZrCI4 and 2-aminobenzenetricar- boxylic acid. This method is simpler and more efficient than previously reported step-by-step method in which magnets were consecutively dispersed in DMF solutions each containing one MOF precursor, and the obtained Fe304@UiO-66-NH2 with three assembly cycles has a higher degree of crystallinity and porosiW. The core-shell Fe3O4@UiO-66-NH2 is highly active and selective in Knoevenagel condensations because of the bifunctionality of UiO-66-NH2 and better mass transfer in the nano-sized shells. It also has good recycling stability, and can be recovered magnetically and reused at least four times without significant loss of catalytic activity and framework integrity. The effects of substitution on the reactivity of benzaldehyde and of substrate size were also investigated.

Silica supported perchloric acid(HClO_4-SiO_2):A mild,reusable and highly efficient heterogeneous catalyst for the synthesis of amidoalkyl naphthols

An efficient and direct procedure has been developed for the preparation of amidoalkyl naphthols by a one-pot condensation of aryl aldehydes, 2-naphthol and urea or amides, in the presence of HClO4-SiO2 as a heterogeneous catalyst. The reactions were carried out under reflux and solvent-free conditions. The present methodology offers several advantages such as excellent yields, simple procedure, easy work-up and ecofriendly reaction condition. The catalyst is easily prepared, stable, reusable and efficient under the reaction conditions.

Membrane enhanced COD degradation of pulp wastewater using Cu_2O/H_2O_2 heterogeneous Fenton process

Both activity and stability of the catalyst can be improved in heterogeneous Fenton reaction,in particular,with no limitation for the working p H and no production of the sludge.In this work,a combination of catalyst Cu_2O and pore-channel-dispersed H_2O_2is proposed to treat the pulp wastewater.Degradation degree of CODs in the wastewater was up to 77%in the ceramic membrane reactor using Cu_2O powder(2.0 g·L^(-1))and membranefeeding H_2O_2(0.8 ml·L^(-1))within 60 min.Evolution of·OH radical formation in the advanced oxidation process was analyzed with a fluorescent method.Utilization efficiency of H_2O_2was successfully enhanced by 10%with the membrane distributor.Further on,the catalyst recyclability was evaluated in a five-cycle test.The concentration of copper ions being dissolved in the treated water was monitored with ICP.After Cu_2O/H_2O_2(membrane)treatment the effluent is qualified to discharge with COD concentration lower than 15 mg·L^(-1)with regard to the national standard GB25467-2010.

Heterogeneous interfacial engineering of Pd/TiO2 with controllable carbon content for improved direct synthesis efficiency of H2O2

Series of heterogeneous interfacial engineered TiO2(C-TiO2) with controllable carbon content were facilely synthesized by incipient-wet impregnation using glucose and subsequent thermal carbonization. The obtained C-TiO2 were used as catalytic supports to load Pd nanoparticles for H2 O2 direct synthesis from H2 and O2. The as-prepared samples were systematically studied by transmission electron microscopy(TEM), X-ray photoelectron spectroscopy(XPS), air isothermal microcalorimeter, temperature-programmed reduction of H2(H2-TPR), and so on. The catalytic results showed that H2 O2 productivity and H2O2 selectivity of Pd/C-TiO2 firstly rose with increasing carbon content and then declined. Pd/C-TiO2 catalyst with 1.89 wt% of carbon content showed the best catalytic performance that had 61.2% of selectivity and 2192 mmol H2O2/g Pd/h of productivity, which were significantly better than those of pristine Pd/TiO2(45.2% and 1827 mmol H2O2/g Pd/h). Various characterization results displayed that the carbon species were heterogeneously dispersed on TiO2 surface. Moreover, no obvious geometric transformation in supports and Pd nanoparticles were observed among different catalysts. The superficial hydrophobicity of Pd/C-TiO2 was gradually promoted with increasing carbon content, which led to the corresponding decrease in adsorption energy of H2O2 with catalysts. According to structure-performance relationship analyses, the heterogeneous interfacial engineering of carbon could maintain the interaction of Pd nanoparticles with TiO2 and simultaneously accelerate the H2O2 desorption. Both factors further determined the excellent H2O2 direct synthesis performance of Pd/C-TiO2.

In-situ/operando techniques to identify active sites for thermochemical conversion of CO_(2) over heterogeneous catalysts

The catalytic conversion of CO_(2) to fuels or chemicals is considered to be an effective pathway to mitigate the greenhouse effect. To develop new types of efficient and durable catalysts, it is critical to identify the catalytic active sites, surface intermediates, and reaction mechanisms to reveal the relationship between the active sites and catalytic performance. However, the structure of a heterogeneous catalyst usually dynamically changes during reaction, bringing a great challenge for the identification of catalytic active sites and reaction pathways. Therefore, in-situ/operando techniques have been employed to real-time monitor the dynamic evolution of the structure of active sites under actual reaction conditions to precisely build the structure–function relationship. Here, we review the recent progress in the application of various in-situ/operando techniques in identifying active sites for catalytic conversion of CO_(2) over heterogeneous catalysts. We systematically summarize the applications of various optical and X-ray spectroscopy techniques, including Raman spectroscopy, Fourier transform infrared (FTIR) spectroscopy, X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), and X-ray absorption spectroscopy (XAS), in identifying active sites and determining reaction mechanisms of the CO_(2) thermochemical conversion with hydrogen and light alkanes over heterogeneous catalysts. Finally, we discuss challenges and opportunities for the development of in-situ characterization in the future to further enlarge the capability of these powerful techniques.

Energy-Efficient Resource Allocation for Heterogeneous Network with Grouping D2D

In this paper,a new communication model is built named grouping D2D(GD2D).Different from the traditional D2D coordination,we proposed GD2D communication in licensed and unlicensed spectrum simultaneously.We formulate a resource allocation problem,which aims at maximizing the energy efficiency(EE)of the system while guaranteeing the quality-of-service(Qos)of users.To efficiently solve this problem,the non-convex optimization problem is first transformed into a convex optimization problem.By transforming the fractional-form problem into an equivalent subtractive-form problem,an iterative power allocation algorithm is proposed to maximize the system EE.Moreover,the optimal closedform power allocation expressions are derived by the Lagrangian approach.Simulation results show that our algorithm achieves higher EE performance than the traditional D2D communication scheme.

Energy-Efficient User Association in Heterogeneous Networks with M2M/H2H Coexistence under QoS Guarantees

In this paper, we propose an energy efficient user association scheme for uplink heterogeneous networks with machine-to-machine(M2M) and human-to-human(H2H) coexistence. A group based random access protocol is designed for massive number of machine-typecommunications(MTC) user equipments'(UEs) transmissions. A user association problem for UEs' energy efficiency maximization is formulated considering the HTC UEs' quality of service(QoS) guarantees and load balance among multiple BSs, simultaneously. A distributed iterative algorithm is developed to solve the optimization problem. In addition, the convergence of the proposed algorithm is proved. Simulation results show that our proposed scheme outperforms other schemes in terms of energy efficiency and QoS guarantees.

Covalently anchored sulfonic acid on silica gel(SiO_2-R-SO_3H)as an efficient and reusable heterogeneous catalyst for the one-pot synthesis of 1,8-dioxooctahydroxanthenes under solvent-free conditions

A highly efficient one-pot synthesis of 1,8-dioxooctahydroxanthenes under solvent-free conditions catalyzed by sulfonic acid covalently anchored onto the surface of silica gel is reported. All types of aldehydes, including aromatic, unsaturated, and heterocyclic, are used. The silica gel/sulfonic acid catalyst （SiO2-R-SO3H） is completely heterogeneous and can be recycled.

GPSA:A Greedy Pull-based Scheduling Approach for P2P Live Streaming under Heterogeneous Environments

Pull-based P2P live streaming is a promising solution for the large scale streaming systems, like PPStream, PPlive, due to its high scalability, low cost and high resilience. However, they usually suffer from bad delay performance. In this paper, we seek to improve the delay performance under ensuring video display quality stemming from chunk scheduling. And so we model Pull-based chunk scheduling problem as a multi-objective optimization problem to minimize the video delay and maximize video display quality in the environment of heterogeneous upload bandwidths, heterogeneous and dynamic propagation delays. Finally we put up with a greedy Pull-based scheduling approach(GPSA) to solve the optimization problem. The evaluation shows GPSA can outperform two classical chunk scheduling approaches and adapt to dynamic variance of propagation delays.

Influence of reservoir heterogeneity on immiscible water-alternating-CO_(2)flooding:A case study

Currently,limited studies of immiscible water-alternating-CO_(2)(imWACO_(2))flooding focus on the impact of reservoir heterogeneity on reservoir development outcomes.Given this,using the heterogeneous reservoirs in the Gao 89-1 block as a case study,this study conducted slab core flooding experiments and numerical simulations to assess the impact of reservoir heterogeneity on imWACO_(2)flooding efficiency.It can be concluded that imWACO_(2)flooding can enhance the sweep volume and oil recovery compared to continuous CO_(2)flooding.As the permeability difference increases,the difference in the swept volume between zones/layers with relatively high and low permeability increases.To optimize the exploitation of reservoirs in the Gao 89-1 block,the optimal timing and CO_(2)injection rate for imWACO_(2)flooding are determined at water cut of 40%and 10000 m^(3)/d,respectively.A short injection-production semi-period,combined with multiple cycles of water and CO_(2)injection alternations,is beneficial for enhanced oil recovery from imWACO_(2)flooding.

SiO_2 AS HETEROGENEOUS NUCLEI OF INTERGROWTH EUTECTIC IN MODIFIED AS-CAST MEDIUM MANGANESE STEEL

By calculation of thermodynamics,analysis of crystal structure and study of TEM and eletron probe,it is first discovered that SiO2 can be acted as one of the heterogeneous nu- clei for lamellar intergorowth eutectic(austenite and cementite)crystallizing in modified as-cast medium manganese steel.

Cobalt‐N_(4) macrocyclic complexes for heterogeneous electrocatalysis of the CO_(2) reduction reaction

Metal-N_(4)(M-N_(4))macrocyclic complexes are interesting electrocatalysts due to their well-defined structures and rich molecular tuning.Among them,metal phthalocyanines have been widely studied for the carbon dioxide reduction reaction(CO_(2)RR)in heterogeneous systems and demonstrated good electrocatalytic performance.However,other complexes like metal corroles and metal porphyrins are much less explored,and often show inferior performances.In this study,three cobalt macrocyclic complexes,cobalt phthalocyanine,cobalt meso-tetraphenylporphyrin,and cobalt meso-triphenylcorrole(CoPc,CoTPP and CoTPC)are investigated in heterogeneous electrocatalysis of CO_(2)RR.Although CoPc/carbon nanotube(CNT)hybrid exhibits high electrocatalytic activity,CNT hybridization does not work for CoTPC and CoTPP that hold weak interactions with CNTs.By the drop-dry method with a high molecular loading of 5.4×10^(–7) mol cm^(–2),CoTPC and CoTPP could deliver appreciable electrode activities.Poly(4-vinylpyridine)(PVP)introduction is further demonstrated as a facile method to afford enhanced activities for CoTPP at low molecular loadings through enhancing molecule-substrate interactions.The partial current density of carbon monoxide for CoTPP+CNT/PVP is around 8 times higher than the sample without PVP at–0.67 V versus reversible hydrogen electrode.This work provides solutions to enhance the electrode activities of molecular electrocatalysts with weak substrate interactions in heterogeneous systems.

Novel HBD-Containing Zn (dobdc) (datz) as efficiently heterogeneous catalyst for CO_(2) chemical conversion under mild conditions

A novel Zn-based metal–organic framework Zn(dobdc)(datz)[Zn_(2)(H2dobdc)(datz)2$1.5DMF]with plentiful hydrogen bond donors(HBD)groups was facilely synthesized from mixed ligands.The dual activation of metal Zn sites and HBD groups for epoxides by forming Zn–O adduct and hydrogen bonds facilitated the ring-opening of epoxide substrate,which is critical for the subsequent CO_(2) fixation.Also,the existence of micropores and N-rich units in Zn(dobdc)(datz)afforded affinity towards CO_(2),which is beneficial to further improvement on catalytic CO_(2) conversion performance.Satisfactorily,Zn(dobdc)(datz)/Bu4NBr system was proved efficient heterogeneous catalyst for the CO_(2) cycloaddition with epoxides,and 98%propylene carbonate yield was obtained under mild conditions(80C,1.5 MPa and solvent-free).In addition,Zn(dobdc)(datz)/Bu4NBr exhibited remarkable versatility to different epoxides and could be completely recycled over six runs with high catalytic activity.The highly stable,easily recycle and solvent-free Zn-based MOF reported here displays eco-friendly and efficient performance to CO_(2)conversion.

The heterodimeric structure of heterogeneous nuclear ribonucleoprotein C1/C2 dictates 1,25-dihydroxyvitamin D-directed transcriptional events in osteoblasts

Heterogeneous nuclear ribonucleoprotein （hnRNP） C plays a key role in RNA processing but also exerts a dominant negative effect on responses to 1,25-dihydroxyvitamin D （1,25（OH）2D） by functioning as a vitamin D response element-binding protein （VDRE-BP）. hnRNPC acts a tetramer of hnRNPC1 （huC1） and hnRNPC2 （huC2）, and organization of these subunits is critical to in vivo nucleic acid-binding. Overexpression of either huC1 or huC2 in human osteoblasts is sufficient to confer VDRE-BP suppression of 1,25（OH）2D-mediated transcription. However, huC1 or huC2 alone did not suppress 1,25（OH）2D-induced transcription in mouse osteoblastic cells. By contrast, overexpression of huC1 and huC2 in combination or transfection with a bone-specific polycistronic vector using a ＂self-cleaving＂ 2A peptide to co-express huC1/C2 suppressed 1,25D-mediated induction of osteoblast target gene expression. Structural diversity of hnRNPC between human/NWPs and mouse/rat/rabbit/dog was investigated by analysis of sequence variations within the hnRNP CLZ domain. The predicted loss of distal helical function in hnRNPC from lower species provides an explanation for the altered interaction between huC1/C2 and their mouse counterparts. These data provide new evidence of a role for hnRNPC1/C2 in 1,25（OH）2D-driven gene expression, and further suggest that species-specific tetramerization is a crucial determinant of its actions as a regulator of VDR-directed transactivation.

Type 2 diabetes in children and adolescents:Exploring the disease heterogeneity and research gaps to optimum management

Over the past 20 years,the incidence and prevalence of type 2 diabetes mellitus(T2DM)in children and adolescents have increased,particularly in racial and ethnic minorities.Despite the rise in T2DM in children and adolescents,the pathophysiology and progression of disease in this population are not clearly understood.Youth-onset T2DM has a more adverse clinical course than is seen in those who develop T2DM in adulthood or those with T1DM.Furthermore,the available therapeutic options are more limited for children and adolescents with T2DM compared to adult patients,mostly due to the challenges of implementing clinical trials.A better understanding of the mechanisms underlying the development and aggressive disease phenotype of T2DM in youth is important to finding effective prevention and management strategies.This review highlights the key evidence about T2DM in children and adolescents and its current burden and challenges both in clinical care and research activities.

Decoloration and mineralization of yeast wastewater by using Ce-Fe/Al_2O_3 as heterogeneous photo-Fenton catalyst

Decoloration and mineralization of yeast wastewater were investigated by using Ce-Fe/Al2O3 as a heterogeneous photo-Fenton catalyst in fluidized bed reactor in order to solve the problem of yeast wastewater discharge. The experimental results were assessed in terms of total organic carbon（TOC） reduction. The operational and reaction conditions affecting the efficiencies of TOC removal such as initial pH value, H2O2 concentration, catalyst loading and UV power were studied. The results show that TOC is reduced from 347.6 mg/L to 10.8 mg/L, color is changed from 500 units to 0 under the conditions as follows： initial pH value 6. 0, H2O2 concentration of 1. 000 g/L, catalyst loading of 5 g/L, reaction duration of 120 rain and reaction temperature of 30 ℃. The irradiated Ce-Fe/Al2O3 catalyst was complexed with 1,10-phenanthroline and then it was subjected to Fourier transform infrared spectroscopy and diffuse reflectance spectroscopy to confirm the formation of Fe（Ⅱ） in the solid state. Heterogeneous photo-Fenton reaction proves to be effective for the treatment of yeast wastewater.

Chemoselective N-nitrosation of secondary amines under heterogeneous and mild conditions via in situ generation of HNO_2

A wide variety of secondary amines are chemoselectively subjected to N-nitrosation reaction with treatment of citric acid and NaNO2 in the presence of wet SiO2 （50%, w/w） in dichloromethane at room temperatture under heterogeneous conditions. The Nnitrosation method is very simple and products can be easily isolated with good to high yields.