Polyoxometalates@Metal-Organic Frameworks: Synthesis Strategies, Nanostructure Modulation and Application in Biomass Conversion.

Polyoxometalates@metal-organic frameworks (POMs@MOFs) have attracted much attention as multifunctional materials in biomass catalysis. Individual POMs and MOFs are hindered by their respective defects, such as poor stability and single catalytic active site, which make it difficult to realize large-scale applications. However, the combination of POMs and MOFs can be used to maximize the catalytic advantages of each. MOFs with high specific surface area and rich pore structure can effectively stabilize and uniformly disperse POMs, while the introduction of POMs also provides more catalytic possibilities for POMs@MOFs. Therefore, POMs@MOFs with ultra-high porosity, large specific surface area and excellent acid catalytic activity have unique catalytic advantages in the field of biomass catalytic conversion. In this work, we provide an overview of the current development of POMs@MOFs in the field of biomass catalysis. The synthesis strategies of POMs@MOFs are summarized and discussed, highlighting the in-situ synthesis methods. We focus on the nanostructure engineering of POMs@MOFs, and explore the "structure-property" relationship in depth. In addition, the representative work of POMs@MOFs in the catalysis of biomass derivatives is summarized. Filially, the prospects, and challenges for the future development of POMs@MOFs in the field of biomass catalysis are also presented.

Non-Noble Metal Catalysts for Electrooxidation of 5-Hydroxymethylfurfural.

2,5-Furandicarboxylic acid (FDCA) is a class of valuable biomass-based platform compounds. The creation of FDCA involves the catalytic oxidation of 5-hydroxymethylfurfural (HMF). As a novel catalytic method, electrocatalysis has been utilized in the 5-hydroxymethylfurfural oxidation reaction (HMFOR). Common noble metal catalysts show catalytic activity, which is limited by price and reaction conditions. Non-noble metal catalyst is known for its environmental friendliness, affordability and high efficiency. The development of energy efficient non-noble metal catalysts plays a crucial role in enhancing the HMFOR process. It can greatly upgrade the demand of industrial production, and has important research significance for electrocatalytic oxidation of HMF. In this paper, the reaction mechanism of HMF undergoes electrocatalytic oxidation to produce FDCA are elaborately summarized. There are two reaction pathways and two oxidation mechanisms of HMFOR discussed deeply. In addition, the speculation on the response of the electrode potential to HMFOR is presented in this paper. The main non-noble metal electrocatalysts currently used are classified and summarized by targeting metal element species. Finally, the paper focus on the mechanistic effects of non-noble metal catalysts in the reaction, and provide the present prospects and challenges in the electrocatalytic oxidation reaction of HMF.

Transition metal phosphides: synthesis nanoarchitectonics, catalytic properties, and biomass conversion applications.

Developing inexpensive and efficient catalysts for biomass hydrogenation or hydrodeoxygenation (HDO) is essential for efficient energy conversion. Transition metal phosphides (TMPs), with the merits of abundant active sites, unique physicochemical properties, tunable component structures, and excellent catalytic activities, are recognized as promising biomass hydrogenation or HDO catalytic materials. Nevertheless, the biomass hydrogenation or HDO catalytic applications of TMPs are still limited by various complexities and inherent performance bottlenecks, and thus their future development and utilization remain to be systematically sorted out and further explored. This review summarizes the current popular strategies for the preparation of TMPs. Subsequently, based on the structural and electronic properties of TMPs, the catalytic activity origins of TMPs in biomass hydrogenation or HDO is elucidated. Additionally, the application of TMPs in efficient biomass hydrogenation or HDO catalysis, as well as highly targeted multiscale strategies to enhance the catalytic performance of TMPs, are comprehensively described. Finally, large-scale amplification synthesis, rational construction of TMP-based catalysts and in-depth study of the catalytic mechanism are also mentioned as challenges and future directions in this research field. Expectedly, this review can provide professional and targeted guidance for the rational design and practical application of TMPs biomass hydrogenation or HDO catalysts.

CeO2-Based Frustrated Lewis Pairs via Defective Engineering: Formation Theory, Site Characterization, and Small Molecule Activation.

Activation of small molecules is considered to be a central concern in the theoretical investigation of environment- and energy-related catalytic conversions. Sub-nanostructured frustrated Lewis pairs (FLPs) have been an emerging research hotspot in recent years due to their advantages in small molecule activation. Although the progress of catalytic applications of FLPs is increasingly reported, the fundamental theories related to the structural formation, site regulation, and catalytic mechanism of FLPs have not yet been fully developed. Given this, it is attempted to demonstrate the underlying theory of FLPs formation, corresponding regulation methods, and its activation mechanism on small molecules using CeO2 as the representative metal oxide. Specifically, this paper presents three fundamental principles for constructing FLPs on CeO2 surfaces, and feasible engineering methods for the regulation of FLPs sites are presented. Furthermore, cases where typical small molecules (e.g., hydrogen, carbon dioxide, methane oxygen, etc.) are activated over FLPs are analyzed. Meanwhile, corresponding future challenges for the development of FLPs-centered theory are presented. The insights presented in this paper may contribute to the theories of FLPs, which can potentially provide inspiration for the development of broader environment- and energy-related catalysis involving small molecule activation.

Hollow Nanoreactors for Controlled Photocatalytic Behaviors: Fundamental Theory, Structure-Performance Relationship, and Catalytic Advantages.

Hollow nanoreactors (HoNRs) have regarded as an attractive catalytic material for photocatalysis due to their exceptional capabilities in enhancing light harvesting, facilitating charge separation and transfer, and optimizing surface reactions. Developing novel HoNRs offers new options to realize controllable catalytic behavior. However, the catalytic mechanism of photocatalysis occurring in HoNRs has not yet been fully revealed. Against this backdrop, this review elaborates on three aspects: 1) the fundamental theoretical insights of HoNRs-driven photocatalytic kinetics; 2) structure-performance relationship of HoNRs to photocatalysis; 3) catalytic advantages of HoNRs in photocatalytic applications. Specifically, the review focuses on the fundamental theories of HoNRs for photocatalysis and their structural advantages for strengthening light scattering, promoting charge separation and transfer, and facilitating surface reaction kinetics, and the relationship between key structural parameters of HoNRs and their photocatalytic performance is in-depth discussed. Also, future prospects and challenges are proposed. It is anticipated that this review paper will pave the way for forthcoming investigations in the realm of HoNRs for photocatalysis.

Reductive Amination of Levulinic Acid to Pyrrolidones: Key Step in Biomass Valorization towards Nitrogen-Containing Chemicals.

Nowadays, the field of biomass conversion is gradually moving towards an encouraging stage. The preparation of nitrogen-containing chemicals using various biomass resources instead of fossil resources do not only reduce carbon emissions, but also diversify the products of biomass conversion, thus increasing the economic competitiveness of biomass refining systems. Levulinic acid (LA) can be used as a promising intermediate in biomass conversion for further synthesis of pyrrolidone via reductive amination. However, there are still many critical issues to be solved. Particularly, the specific effects of catalysts on the performance of LA reductive amination have not been sufficiently revealed, and the potential impacts of key conditional factors have not been clearly elucidated. In view of this, this review attempts to provide theoretical insights through an in-depth interpretation of the above key issues. The contribution of catalysts to the reductive amination of LA as well as the catalyst structural preferences for improving catalytic performance are discussed. In addition, the role of key conditional factors is discussed. The insights presented in this review will contribute to the design of catalyst nanostructures and the rational configuration of green reaction conditions, which may provide inspiration to facilitate the nitrogen-related transformation of more biomass platform molecules.

Molecular Diffusion in Nanoreactors' Pore Channel System: Measurement Techniques, Structural Regulation, and Catalytic Effects.

Nanoreactors, as a new class of materials with highly enriched and ordered pore channel structures, can achieve special catalytic effects by precisely identifying and controlling the molecular diffusion behavior within the ordered pore channel system. Nanoreactors-driven molecular diffusion within the ordered pore channels can be highly dependent on the local microenvironment in the nanoreactors' pore channel system. Although the diffusion process of molecules within the ordered pore channels of nanoreactors is crucial for the regulation of catalytic behaviors, it has not yet been as clearly elucidated as it deserves to be in this study. In this review, fundamental theory and measurement techniques for molecular diffusion in the pore channel system of nanoreactors are presented, structural regulation strategies of pore channel parameters for controlling molecular diffusion are discussed, and the effects of molecular diffusion in the pore channel system on catalytic reactivity and selectivity are further analyzed. This article attempts to further develop the underlying theory of molecular diffusion within the theoretical framework of nanoreactor-driven catalysis, and the proposed perspectives may contribute to the rational design of advanced catalytic materials and the precise control of complex catalytic kinetics.

Regional CO2 accounting and market layout of incinerator fly ash management in China.

The reduction of greenhouse gas (GHG) emissions from solid waste incinerator fly ash (IFA) management attracts growing interests since China's zero-waste plan and carbon peak/neutral goals. Herein, provincial GHG emissions from four demonstrated IFA reutilization technologies in China were estimated after analyzing IFA spatial-temporal distribution. Results indicate that technologies transition (landfilling-to-reutilization) could reduce GHG except for glassy slag production. IFA to cement option could potentially realize negative GHG emissions. Spatial GHG variation drivers in IFA management were recognized as provincial-different IFA composition and power emission factors. IFA management options were recommended provincially after weighting local development goals related to GHG reduction and economic benefits. Baseline scenario analysis shows that China's IFA industry would reach carbon peak in 2025 (5.02 Mt). 2030's GHG reduction potential (6.12 Mt) is equivalent to that of absorbed CO2 by 340 million trees annually. Overall, this research could contribute to illustrating future market layout complying with carbon peaking.

Catalytic hydrothermal carbonization of wet organic solid waste: A review.

Hydrothermal carbonization has gained attention in converting wet organic solid waste into hydrochar with many applications such as solid fuel, energy storage material precursor, fertilizer or soil conditioner. Recently, various catalysts such as organic and inorganic catalysts are employed to guide the properties of the hydrochar. This review presents a summarize and a critical discussion on types of catalysts, process parameters and catalytic mechanisms. The catalytic impact of carboxylic acids is related to their acidity level and the number of carboxylic groups. The catalysis level with strong mineral acids is likely related to the number of hydronium ions liberated from their hydrolysis. The impact of inorganic salts is determined by the Lewis acidity of the cation. The metallic ions in metallic salts may incorporate into the hydrochar and increase the ash of the hydrochar. The selection of catalysts for various applications of hydrochars and the environmental and the techno-economic aspects of the process are also presented. Although some catalysts might enhance the characteristics of hydrochar for various applications, these catalysts may also result in considerable carbon loss, particularly in the case of organic acid catalysts, which may potentially ruin the overall advantage of the process. Overall, depending on the expected application of the hydrochar, the type of catalyst and the amount of catalyst loading requires careful consideration. Some recommendations are made for future investigations to improve laboratory-scale process comprehension and understanding of pathways as well as to encourage widespread industrial adoption.

One-Pot Tandem Transformation of Inulin as Fructose-Rich Platform Towards 5-Hydroxymethylfurfural: Feedstock Advantages, Acid-Site Regulation and Solvent Effects.

The valorization of non-grain biomass feedstocks to value-added chemicals, polymers and alternative fuels is a crucial route for the utilization of renewable resources. Inulin belongs to a type of fructans, which is a pivotal platform bridging upstream fructose-rich biomass feedstocks typically represented by Jerusalem artichoke and downstream platform molecules such as alcohols, aldehydes and acids. Fructose can be directly obtained from the inulin hydrolysis and further converted into various platform chemicals, which is a more environmentally economical route than the conventional catalytic upgrading of cellulose. Nevertheless, most perspectives over the last decade have focused on the valorization of cellulose-derived carbohydrates, without much emphasis on the practical importance of one-pot transformation of inulin. In this review, we aim to demonstrate an efficient one-pot tandem transformation system of the inulin as fructose-rich platform towards 5-hydroxymethylfurfural (HMF). Core concerns are placed on elucidating the contributing roles of acid sites and solvents in enhancing the overall catalytic performance. The perspectives presented in this review may contribute to the innovation in the catalytic refining of fructose-rich non-grain biomass and the development of a greener biomass-based energy system.

Kinetics Driven by Hollow Nanoreactors: An Opportunity for Controllable Catalysis.

As a novel class of catalytic materials, hollow nanoreactors offer new opportunities for improving catalytic performance owing to their higher controllability on molecular kinetic behavior. Nevertheless, to achieve controllable catalysis with specific purposes, the catalytic mechanism occurring inside hollow nanoreactors remains to be further understood. In this context, this Review presents a focused discussion about the basic concept of hollow nanoreactors, the underlying theory for hollow nanoreactor-driven kinetics, and the intrinsic correlation between key structural parameters of hollow nanoreactors and molecular kinetic behaviors. We aim to provide in-depth insights into understanding kinetics occurred within typical hollow nanoreactors. The perspectives proposed in this paper may contribute to the development of the fundamental theoretical framework of hollow nanoreactor-driven catalysis.

Environmental, economic, and energy analysis of municipal solid waste incineration under anoxic environment in Tibet Plateau.

The first Municipal solid waste incineration (MSWI) plant in Lhasa, Tibet, the plateau region of China, started its operation in 2018. Considering the elevation and extreme climate (low pressure and low oxygen content) in Tibet, noticeable differences may be envisaged compared to MSWI elsewhere. The aim of this study is to evaluate the environmental impacts, economic benefits, and energy efficiency of this MSWI project with three representative MSWI case in plain region using Life cycle assessment (LCA), Cost-benefit analysis (CBA), and energy analysis methods. The result showed that enhancing blast volume and cross-sectional area of the boiler help adapt to the oxygen-deficient environment. GaBi model was employed based on the CML 2001 methodology to perform LCA. LCA shows that the Lhasa MSWI project has lower positive environment impacts than the projects in plain region. More attention is needed for the deficiencies in flue gas emissions of MSWI in the plateau region. CBA shows that the payback period is 11.97 years and the internal rate of return is 8.75%. The energy analysis indicates that the boiler energy efficiency is up to 81.92%. MSWI subject to minor changes seems suitable to Tibetan plateau, and can be deployed further.

Solvent Effects Enable Efficient Tandem Conversion of Cellulose and Its Monosaccharides Towards 5-Hydroxymethylfurfural.

The biomass-derived platform compound 5-hydroxymethylfurfural (HMF) has been hailed as the "Sleeping Giant" due to its promising applications, and it occupies a critical spot in the biomass upgrading roadmap. HMF is typically produced from cellulose and its monosaccharides via a complex tandem conversion with multiple steps (i. e., cellulose depolymerization, glucose isomerization, fructose dehydration, etc.). Previous investigations have confirmed the irreplaceable contribution of solvents in regulating the tandem conversion of cellulose and its monosaccharides to HMF. However, the potential effects of solvents in contributing to this multi-step tandem process have not yet been clearly elucidated. In this context, this Review aims to provide in-depth insights into the intrinsic interactions between solvent system and substrate conversion (cellulose and its monosaccharides conversion), reaction regulation (reaction activity and selectivity regulation), as well as product acquisition (humins formation inhibition and product purification). It attempts to elucidate specific solvent effects to promote a more efficient tandem conversion of cellulose and its monosaccharides towards HMF. The insights provided in this Review may contribute to a more sustainable HMF production from biomass feedstocks and a further development of greener solvent systems.

Co-Expression of Pig IL-2 and Fusion Bovine Cathelicidin Gene by Recombinant Plasmids in Yeast and Their Promotion of Mouse Antibacterial Defense.

In order to develop an effective and safe immunomodulator to enhance the antimicrobial bioactivity and immunity of animals against infectious bacterial diseases, a recombinant plasmid pGAPZαA-IL2-B co-expressing pig interleukin-2 (PIL-2) and fused bovine cathelicidin (FBC) genes were constructed using the 2A self-cleavage technique. After being expressed in Pichia pastoris strain SMD1168, the recombinant yeast was administered orally to 5-week-old female ICR mice. The control mice were similarly dosed with P. pastoris with a blank plasmid or FBC recombinant plasmid alone. At 28 days post-treatment, the mice were challenged intraperitoneally with virulent strains of either E. coli or S. aureus. Compared with the control groups, the mice that received recombinant yeast co-expressing PIL-2/FBC manifested significant increases in the number of leukocytes, CD4+ and CD8+ T cells, IgG, and the gene expressions of TLRs(TLR1,4,6,9), antimicrobial peptides(CRP4 and CRAMP) and cytokines (IL-2, 4, 6, 7, 12, 15, 23, IFN-γ, and TNF-α) in the blood. Furthermore, the treated mice displayed significantly higher survival than the other two control groups after the challenge. These results suggest that the antimicrobial activity and immunity of animals can be effectively enhanced by the in vivo co-expression of IL-2 and the FBS gene, which can facilitate the development of new immunopotentiation molecules to overcome the infection of antibiotic-resistant bacteria.

Dynamic changes of microbial community and moisture ratio during bio-drying of sludge after electro-dewatering.

Using electro-dewatering as the pretreatment process for sludge bio-drying can improve the dewatering performance. It was innovatively investigated including the microbial mechanism and the kinetics of moisture removal by bio-drying with electro-dewatered sludge in this study. Two bio-drying processes using electro-dewatered sludge (EDS) and sludge added cornstalk conditioner (CSS) were compared. Microbial community analysis showed that the abundance of Bacteroidetes increased from 4.21% to 16.67% after electro-dewatering. The dominant phyla were Bacteroidetes (36.79%), Proteobacteria (32.35%), and Actinobacteria (24.58%) at the end of EDS bio-drying. Network analysis revealed that the co-occurrence patterns in EDS included 40 nodes and 97 edges. The prediction results of the Kyoto Encyclopedia of Genes and Genomes demonstrated that the relative abundances of carbohydrate metabolism and metabolism of terpenoids and polyketides in sludge decreased, while the relative abundances of lipid metabolism, xenobiotic biodegradation and metabolism increased after electro-dewatering. Five thin layer drying kinetic models were analyzed to estimate the bio-drying kinetic parameters. The Page's model could be better fitted to the results and the highest R2 was 0.9570 in the EDS. The new coefficients k (0.1637) and n (1.2097) were obtained. The results provided mechanism and data support for exploring and applying bio-drying technology after sludge electro-dewatering.

Synthesis of Hierarchical-Porous Fluorinated Metal-Organic Frameworks with Superior Toluene Adsorption Properties.

Constructing metal-organic frameworks (MOFs) with high volatile organic compounds (VOCs) adsorption capacity and excellent water resistance remain challenging. Herein, a monocarboxylic acid-assisted mixed ligands strategy was designed to synthesize a novel fluorinated MOFs, MIL-53 (Al). The monocarboxylic acid promoted crystallization and produced abundant crystal defects, which increased pore volume. Moreover, the competitive coordination between tetrafluoroterephthalic acid and 1,4-dicarboxybenzene was moderated by monocarboxylic modulators, significantly improving the hydrophobicity. The toluene uptake of the optimal sample reached 254.85 mg g-1 under humid conditions, increased by 33.56 % of MIL-53(Al), and the QWet /QDry (the ratio of adsorption quality under wet to adsorption quality under dry) was 0.92, remarkably surpassing that of origin MIL-53 (0.72). The recycle experiment showed superior reusability with no performance degradation after 10 recycle under RH=50 % (relative humidity). The adsorptive kinetic and thermodynamic analysis proves that the adsorption process is controlled by surface mono-layer adsorption and pore diffusion. The fluorine group affects the internal diffusion, which weakens the transfer rate. This strategy opens a new prospect of obtaining hierarchical functional MOFs for meeting the VOCs uptake under the practical application.

Alloy-Driven Efficient Electrocatalytic Oxidation of Biomass-Derived 5-Hydroxymethylfurfural towards 2,5-Furandicarboxylic Acid: A Review.

In recent years, electrocatalysis was progressively developed to facilitate the selective oxidation of biomass-derived 5-hydroxymethylfurfural (HMF) towards the value-added chemical 2,5-furandicarboxylic acid (FDCA). Among reported electrocatalysts, alloy materials have demonstrated superior electrocatalytic properties due to their tunable electronic and geometric properties. However, a specific discussion of the potential impacts of alloy structures on the electrocatalytic HMF oxidation performance has not yet been presented in available Reviews. In this regard, this Review introduces the most recent perspectives on the alloy-driven electrocatalysis for HMF oxidation towards FDCA, including oxidation mechanism, alloy nanostructure modulation, and external conditions control. Particularly, modulation strategies for electronic and geometric structures of alloy electrocatalysts have been discussed. Challenges and suggestions are also provided for the rational design of alloy electrocatalysts. The viewpoints presented herein are anticipated to potentially contribute to a further development of alloy-driven electrocatalytic oxidation of HMF towards FDCA and to help boost a more sustainable and efficient biomass refining system.

Ultrafine Ruthenium Clusters Shell-Embedded Hollow Carbon Spheres as Nanoreactors for Channel Microenvironment-Modulated Furfural Tandem Hydrogenation.

Rationally modulating the catalytic microenvironment is important for targeted induction of specific molecular behaviors to fulfill complicated catalytic purposes. Herein, a metal pre-chelating assisted assembly strategy is developed to facilely synthesize the hollow carbon spheres with ultrafine ruthenium clusters embedded in pore channels of the carbon shell (Ru@Shell-HCSs), which can be employed as nanoreactors with preferred electronic and geometric catalytic microenvironments for the efficient tandem hydrogenation of biomass-derived furfural toward 2-methylfuran. The channel-embedding structure is proved to confer the ultrafine ruthenium clusters with an electron-deficient property via a reinforced interfacial charge transfer mechanism, which prompts the hydrogenolysis of intermediate furfuryl alcohol during the tandem reaction, thus resulting in an enhanced 2-methylfuran generation. Meanwhile, lengthening the shell pore channel can offer reactant molecules with a prolonged diffusion path, and correspondingly a longer retention time in the channel, thereafter delivering an accelerated tandem hydrogenation progression. This paper aims to present a classic case that emphasizes the critical role of precisely controlling the catalytic microenvironment of the metal-loaded hollow nanoreactors in coping with the arduous challenges from multifunctional catalyst-driven complex tandem reactions.

Recent Advances of Chlorinated Volatile Organic Compounds' Oxidation Catalyzed by Multiple Catalysts: Reasonable Adjustment of Acidity and Redox Properties.

The severe hazard of chlorinated volatile organic compounds (CVOCs) to human health and the natural environment makes their abatement technology a key topic of global environmental research. Due to the existence of Cl, the byproducts of CVOCs in the catalytic combustion process are complex and toxic, and the possible generation of dioxin becomes a potential risk to the environment. Well-qualified CVOC catalysts should process favorable low-temperature catalytic oxidation ability, excellent selectivity, and good resistance to poisoning, which are governed by the reasonable adjustment of acidity and redox properties. This review overviews the application of different types of multicomponent catalysts, that is, supported noble metal catalysts, transition metal oxide/zeolite catalysts, composite transition metal oxide catalysts, and acid-modified catalysts, for CVOC degradation from the perspective of balance between acidity and redox properties. This review also highlights the synergistic degradation of CVOCs and NOx from the perspective of acidity and redox properties. We expect this work to inspire and guide researchers from both the academic and industrial communities and help pave the way for breakthroughs in fundamental research and industrial applications in this field.