氧化还原驱动的高活性Pd/PdO表面界面促进低温甲烷燃烧

天然气汽车尾气中尚未充分燃烧的甲烷是一种典型的温室气体之一,其温室效应远超二氧化碳,达到后者的20倍以上.因此,减少甲烷的排放对于有效应对气候变化至关重要.目前,以Pd/Al_(2)O_(3)为基础催化剂的催化燃烧反应,已被证实为减少甲烷排放的最为切实可行的技术手段.深入了解钯基催化剂的活性结构不仅有助于合理设计高效的催化体系,还能在很大程度上减少贵金属钯的使用量.然而,在甲烷燃烧反应过程中,由于氧化还原气氛的复杂性,Pd金属的表面容易转变为不同结构,这增加了研究其活性结构的难度.此外,催化剂的制备方法、载体的性质、预处理的气氛以及温度等因素均会对Pd的价态和粒径效应产生影响,使得Pd基催化剂在甲烷燃烧反应中的活性结构至今仍存在争议.为了深入研究这一问题,本文选用商业化的纳米级γ-Al_(2)O_(3)作为载体,采用易于工业化应用的浸渍法制备了Pd/Al_(2)O_(3)催化剂,并研究其在低温(200-400℃)贫燃条件下的活性结构.球差电镜结果表明,催化剂中的Pd纳米颗粒在不同气氛中经800℃高温预处理后呈现出不同的结构特点.氦气处理后的催化剂中,Pd以完全金属态的形式存在;氧气处理后的催化剂中,Pd以PdO的形式存在;甲烷燃烧反应气处理后的催化剂中,PdO大颗粒上存在金属Pd小颗粒,呈现出“荔枝型”Pd/PdO结构.准原位X射线光电子能谱和原位X射线吸收谱等结果表明,“荔枝型”Pd/PdO结构是在甲烷燃烧反应中受氧化还原气氛诱导形成的.该独特的“荔枝型”Pd/PdO结构的催化剂在300℃甲烷燃烧反应中,表现出337.8μmol gPd^(-1) s^(-1)的反应速率,分别是纯金属Pd和PdO型催化剂反应速率的10.7倍和15.5倍.进一步研究表明,无论催化剂中Pd的初始状态为金属态或是氧化态,高活性的“荔枝型”Pd/PdO结构都可以在较低温度(500℃)的长时间(12 h)甲烷燃烧反应中缓慢生成.通过调节预处理气氛中甲烷与氧气的相对浓度,可以实现689.2μmol gPd-1 s^(-1)的反应速率,高于文献已报道的Pd基催化剂在相似反应条件下的活性.密度泛函理论计算结果表明,相对于金属Pd和PdO,甲烷在Pd/PdO界面处表现出最低(0.40 eV)的自由能势垒,这表明由于界面处金属Pd和PdO的协同作用,甲烷断裂第一个C-H键的解离活化过程更容易发生,从而解释了“荔枝型”Pd/PdO结构高催化活性的来源.综上,本文通过先进的球差电镜和原位光谱表征技术,为深入认识甲烷燃烧钯基催化剂活性结构提供了新的角度.研究发现,反应过程中因气氛诱导而生成的高活性结构可能是重要的活性中心,这一观点不仅有助于理解甲烷燃烧反应的机理,而且可以为其他氧化还原催化体系的研究以及工业催化剂的设计制备提供参考.

Upcycling biomass waste into Fe single atom catalysts for pollutant control

Contaminants of heavy metals and antibiotics, which are frequently detected in water, soil and food chains with increasing prevalence in our current society, can cause potential harm to human health and disrupt human ecosystem irreversibly. Herein, we have successfully utilized biomass waste ferns contaminated by iron mines, to fabricate a first-of-its-kind high-performance class of Fe single-atom catalysts(FeSAC) by a facile pyrolysis. The optimal FeSAC-800 shows an excellent efficiency in the fastphotocatalytic degradation of six types of quinolone antibiotics(e.g., norfloxacin, levofloxacin, ciprofloxacin, enrofloxacin, lomefloxacin, flumequine) in 1 h under the simulated natural light irradiation. Based on advanced characterization, a well-defined structure of FeN_(4), confined in the porous carbon is elaborated for the FeSAC-800. Mechanism of the photodegradation is via a Fenton-like oxidation process whereas the reactive oxygen species play a key role. These findings open a new avenue for efficient, sustainable utilization of biomass waste in pollutant control.

Probing the intrinsic catalytic activity of carbon nanotubes for the metal-free oxidation of aromatic thiophene compounds in ionic liquids

A metal-free catalytic system combining oxidized carbon nanotubes (oCNTs) and ionic liquids (ILs) is presented for the oxidation of aromatic thiophene compounds with H2O2 as an oxidant. The oCNTs exhibit impressively high activity and stability in the system, which show an even better performance than those of some reported metal catalysts. The ILs are proved to have indispensable influence on the enhanced catalytic performance of the oCNTs. Detailed characterization by TG-MS and XPS demonstrates that the carbonyl groups are the active sites for the oxidation process, which is further supported by the deactivation and the model catalysts experiments. The quantitative analysis of different oxygen groups in oCNTs could be achieved by an isothermal temperature programmed TG-MS method. The concentration of carbonyl groups is 1.46 mmol per 1 g oCNTs and the tuiriover frequency of oCNTs could also be obtained (10.7 h^-1 in the presence of OmimPF6). H2O2 decomposition experiments combined with the EPR results reveal that the presence of OmimPF6 can avoid the intermediate HO· to form O2 and then improve the catalytic performance of oCNTs for the oxidation of dibenzothiophene.

Dissection of Z-disc myopalladin gene network involved in the development of restrictive cardiomyopathy using system genetics approach

AIM To investigate the regulation of Myopalladin(Mypn) and identify its gene network involved in restrictive cardiomyopathy(RCM).METHODS Gene expression values were measured in the heart of a large family of BXD recombinant inbred(RI) mice derived from C57BL/6J and DBA/2J. The proteomics data were collected from Mypn knock-in and knock-out mice. Expression quantitative trait locus(eQ TL) mapping methods and gene enrichment analysis were used to identify Mypn regulation,gene pathway and co-expression networks.RESULTS A wide range of variation was found in expression of Mypn among BXD strains. We identified upstream genetic loci at chromosome 1 and 5 that modulate the expression of Mypn. Candidate genes within these loci include Ncoa2,Vcpip1,Sgk3,and Lgi2. We also identified 15 sarcomeric genes interacting with Mypn and constructed the gene network. Two novel members of this network(Syne1 and Myom1) have been confirmed at the protein level. Several members in this network are already known to relate to cardiomyopathy with some novel genes candidates that could be involved in RCM. CONCLUSION Using systematic genetics approach,we constructed Mypn co-expression networks that define the biological process categories within which similarly regulated genes function. Through this strategy we have found several novel genes that interact with Mypn that may play an important role in the development of RCM.

Dynamic carbon surface chemistry: Revealing the role of carbon in electrolytic water oxidation

Carbon materials have been widely used as electrodes, but the mechanistic roles are still not clear due to the complexity of the carbon surface chemistry. Herein we clarify that intrinsic material properties of carbon have to be activated by extrinsic factors. Pure carbon has no catalytic activity when used as electrode for electrocatalytic water oxidation. The evolution of oxygen functional groups on the carbon surface with increasing potential and the subsequent formation of real active sites with iron impurities from the electrolyte have been confirmed. These in-situ formed active sites protect the carbon from deep oxidation. This unprecedented finding not only provides insight into the dynamic evolution of carbon electrode surface chemistry and raises awareness of the need for detailed surface analysis under operando conditions, but also suggests a direction for the development of scalable and high-performance carbonbased electrode systems for various electrochemical applications.

Atomically Precise Design of PtSn Catalyst for the Understanding of the Role of Sn in Propane Dehydrogenation

Propane dehydrogenation(PDH),an atom-economic reaction to produce high-value-added propylene and hydrogen with high efficiency,has recently attracted extensive attention.The severe deactivation of Pt-based catalysts through sintering and coking remains a major challenge in this high-temperature reaction.The introduction of Sn as a promoter has been widely applied to improve the stability and selectivity of the catalysts.However,the selectivity and stability of PtSn catalysts have been found to vary considerably with synthesis methods,and the role of Sn is still far from fully understanding.To gain in-depth insights into this issue,we synthesized a series of PtSn/SiO_(2)and SnPt/SiO_(2)catalysts by varying the deposition sequence and Pt:Sn ratios using atomic layer deposition with precise control.We found that PtSn/SiO_(2)catalysts fabricated by the deposition of SnO_(x)first and then Pt,exhibited much better propylene selectivity and stability than the SnPt/SiO_(2)catalysts synthesized the other way around.We demonstrate that the presence of Sn species at the Pt-SiO_(2)interface is of essential importance for not only the stabilization of PtSn clusters against sintering under reaction conditions but also the promotion of charge transfers to Pt for high selectivity.Besides the above,the precise regulation of the Sn content is also pivotal for high performance,and the excess amount of Sn might generate additional acidic sites,which could decrease the propylene selectivity and lead to heavy coke formation.These findings provide deep insight into the design of highly selective and stable PDH catalysts.

Dynamic tracking of exsolved PdPt alloy/perovskite catalyst for efficient lean methane oxidation

Supported Pd based catalysts are considered as the efficient candidates for low-carbon alkane oxidation for their outstanding capability to break C-H bond. Whereas, the irreversible deactivation of Pd based catalysts was still frequently observed. Herein, we reinforced the extruded Pd nanoparticles with quantitive Pt to assemble the evenly distributed Pd Pt nanoalloy onto ferrite perovskite(Pd Pt-LCF) matrix with strengthened robustness of metal/oxide support interface. We further co-achieved the enhanced performance, anti-overoxidation as well as resistance of vapor-poisoning in durability measurement. The operando X-ray photoelectron spectroscopy(O-XPS) combined with various morphology characterizations confirms that the accumulation of surface deep-oxidation species of Pd^(4+) is the culprit for fast activity loss in exsolved Pd system, especially at high temperature of 400 ℃. Conversely, it could be completely suppressed by in-situ alloying Pd with equal amount of Pt, which helps maintain the metastable Pd^(2+)/Pd shell and metallic solid-solution core structure. The density function theory(DFT) calculations further buttress that the dissociation of C–H was facilitated on alloy/perovskite interface which is, on the contrary, resistant toward O–H bond cleavage, as compared to Pd/perovskite. Our work suggests that the modification of exsolved metal/oxide catalytic interface could further enrich the toolkit of heterogeneous catalyst design.