How Absorbed Hydrogen Affects the Catalytic Activity of Transition Metals

Heterogeneous catalysis is commonly governed by surface active sites. Yet, areas just below the surface can also influence catalytic activity, for instance, when fragmentation products of catalytic feeds penetrate into catalysts. In particular, H absorbed below the surface is required for certain hydrogenation reactions on metals. Herein, we show that a sufficient concentration of subsurface hydrogen, H^sub, may either significantly increase or decrease the bond energy and the reactivity of the adsorbed hydrogen, H^ad, depending on the metal. We predict a representative reaction, ethyl hydrogenation, to speed up on Pd and Pt, but to slow down on Ni and Rh in the presence of H^sub, especially on metal nanoparticles. The identified effects of subsurface H on surface reactivity are indispensable for an atomistic understanding of hydrogenation processes on transition metals and interactions of hydrogen with metals in general.     

可控合成具有氧化还原分区的Au-TiO2纳米哑铃光催化剂（英文）

太阳能因其环保清洁和来源丰富的特性被认为是最理想的资源之一.而光催化水分解是将太阳能转化为化学能的众多转换技术中,使用最广泛的策略之一.但H2和O2的逆反应显著降低了光催化水分解的效率,并且在实际应用中需要高昂的气体分离成本.因此,找到一种既可实现光催化有效水分解,同时抑制逆反应的策略具有十分重要的意义.到目前为止,为了实现光生电荷的有效分离,构建一维(1D)异质纳米结构光催化剂,被认为是抑制逆反应最有效的策略之一.其中哑铃状纳米结构,如Au-SiO2,Au-Fe3O4,Cu1.94S-CuS,Au-PbS(PbSe),Cu-Ag,Ag-Fe3O4,在促进光生电荷有效分离方面具有很大优势.但关于上述哑铃状纳米结构材料合成条件相对复杂,生长机理尚不清楚.对此,我们通过一种简便的合成策略制备了Au纳米棒/TiO2纳米哑铃结构光催化剂(Au NRs/TiO2 NDs).TiO2纳米颗粒(NP)仅包裹在Au NRs的两端.由于其独特的结构,可以实现电子空穴的定向分离,并减少它们在光照射下的复合,从而显著地提高电荷分离效率.同时,形成了氧化和还原反应的空间分离区域,从而有效地抑制了逆反应.通过SEM,XRD,和UV-Vis研究了可控合成哑铃状结构形态的关键因素.发现反应温度和酸度对Au NRs末端TiO2的包裹量有显著影响.基于此,我们提出了Au NRs/TiO2 NDs结构光催化剂的合成机理.并且通过改变加入的NaHCO3含量精准调节TiO2在Au NRs两端的包覆量,从而逐步提高Au NRs/TiO2 NDs光催化剂的产氢活性.在不断优化条件下,H2产率可达60264μmol/g/h,大约是报道的Au/TiO2光催化剂6倍.而电化学测试结果显示,在UV光照射下,Au NRs末端TiO2的包裹量越大,光电流相应越大.进一步证明光生电子定向从TiO2注入到Au NRs中,发生还原反应,而空穴留在TiO2上,发生氧化反应,从而实现氧化还原反应的分区.     

Recent advances in Ni−Al bimetallic catalysis for unreactive bond transformation

Ni-Al bimetallic catalysis proves to be an efficient catalytic strategy for unreactive bond transformations. Recently, chiral bifunctional ligands, especially amphoteric secondary phosphine oxide(SPO) ligand, are used for a more powerful synergistic effect in the bimetal-catalyzed reactions, providing not only milder reaction conditions and higher reactivity but also excellent reaction selectivity. Herein, we give a brief review on the development of Ni-Al bimetallic catalytic system and highlight recent advances in enantioselective Ni-Al bimetallic catalysis for unreactive bond transformation.     

Promiscuous catalysis by the tetrahymena group I ribozyme

Catalytic promiscuity, the ability of an enzyme to catalyze alternative reactions, has been suggested to have played an important role in the evolution of new catalytic activities in protein enzymes. Similarly, promiscuous activities may have been advantageous in an earlier RNA world. The Tetrahymena Group I ribozyme naturally catalyzes the site-specific guanosine attack on an anionic phosphate diester and has been shown to also catalyze aminoacyl transfer to water, albeit with a small rate acceleration (<10-fold). This inefficient catalysis could be due to the differences in charge and/or geometry requirements for the two reactions. Herein, we describe a new promiscuous activity of this ribozyme, the site-specific guanosine attack on a neutral phosphonate diester. This alternative substrate lacks the negative charge at the reaction center but, in contrast to the aminoacyl substrate, can undergo nucleophilic attack with the same geometry as the natural substrate. Our results show that the neutral phosphonate reaction is catalyzed about 1 x 106-fold, substantially better than the acyl transfer but far below the normal anionic substrate. We conclude that both charge and geometry are important factors for catalysis of the normal reaction and that promiscuous catalytic activities of ribozymes could have been created or enhanced by reorienting and swapping RNA domains.     

Nanoplasmonic Photoluminescence Spectroscopy at Single‐Particle Level: Sensing for Ethanol Oxidation

Surface plasmon resonances of metal nanoparticles have shown significant promise for the use of solar energy to drive catalytic chemical reactions. More importantly, understanding and monitoring such catalytic reactions at single‐nanoparticle level is crucial for the study of local reaction processes. Herein, using plasmonic photoluminescence (PL) spectroscopy, we describe a novel sensing method for catalytic ethanol oxidation reactions at the single‐nanoparticle level. The Au nanorod monitors the interfacial interaction with ethanol during the catalytic reaction through the PL intensity changes in the single‐particle PL spectra. The analysis of energy relaxation of excited electron–hole pairs indicates the relationship between the PL quenching and ethanol oxidation reaction on the single Au nanorod.     

Disentangling Reaction Processes of Zeolites within Single-Oriented Channels

Establishing structure–reactivity relationships for specific channel orientations of zeolites is vital to developing new, superior materials for various applications, including oil and gas conversion processes. Herein, a well-defined model system was developed to build structure–reactivity relationships for specific zeolite-channel orientations during various catalytic reaction processes, for example, the methanol- and ethanol-to-hydrocarbons (MTH and ETH) process as well as oligomerization reactions. The entrapped and effluent hydrocarbons from single-oriented zeolite ZSM-5 channels during the MTH process were monitored by using operando UV/Vis diffuse reflectance spectroscopy (DRS) and on-line mass spectrometry (MS), respectively. The results reveal that the straight channels favor the formation of internal coke, promoting the aromatic cycle. Furthermore, the sinusoidal channels produce aromatics, (e.g., toluene) that further grow into larger polyaromatics (e.g., graphitic coke) leading to deactivation of the zeolites. This underscores the importance of careful engineering of materials to suppress coke formation and tune product distribution by rational control of the location of zeolite acid sites and crystallographic orientations.     

As Nice as π: Aromatic Reactions Activated by π-Coordination to Transition Metals

π-Coordination of aromatic molecules to metals dramatically alters their reactivity. For example, coordinated carbons become more electrophilic and C−H bonds of coordinated rings become more acidic. For many years, this change in reactivity has been used to trigger reactions that would not take place for uncoordinated arenes, however, there has been a recent resurgence in use of this technique, in part due to the development of catalytic reactions in which π-coordination is transient. In this Minireview, we describe the key reaction chemistry of arenes coordinated to a range of transition metals, including stereoselective reactions and industrially relevant syntheses. We also summarise outstanding examples of catalytic processes. Finally, we give perspectives on the future direction of the field, with respect to both reactions that are stoichiometric in activating metals and those employing catalytic metal.     

DFT-based mechanism for the unexpected formation of dienes in the PtCl2 isomerization of propargylic acetates: examples of inhibition of the Rautenstrauch process

The reactivity of the Pt(II)-mediated processes of unsaturated compounds strongly depends on the substrate structure, and the catalytic activation process may follow different reaction paths, such as skeletal rearrangements, cyclizations, and isomerizations. Herein, we analyze and report the striking effect of an ester group as an alkyne substituent on the reactivity of propargylic enynes, which has been shown to inhibit the expected Rautenstrauch process. The computed results agree with experimental evidence and provide a comprehensible rationalization.     

Catalysis of Radical Reactions: A Radical Chemistry Perspective

The area of catalysis of radical reactions has recently flourished. Various reaction conditions have been discovered and explained in terms of catalytic cycles. These cycles rarely stand alone as unique paths from substrates to products. Instead, most radical reactions have innate chains which form products without any catalyst. How do we know if a species added in “catalytic amounts” is a catalyst, an initiator, or something else? Herein we critically address both catalyst‐free and catalytic radical reactions through the lens of radical chemistry. Basic principles of kinetics and thermodynamics are used to address problems of initiation, propagation, and inhibition of radical chains. The catalysis of radical reactions differs from other areas of catalysis. Whereas efficient innate chain reactions are difficult to catalyze because individual steps are fast, both inefficient chain processes and non‐chain processes afford diverse opportunities for catalysis, as illustrated with selected examples.     

Alkylidene and alkylidyne surface complexes: Precursors and intermediates in alkane conversion processes on supported single-site catalysts

Well-defined surface alkylidenes and alkylidynes can be compared to their molecular counterparts in structural features and formation pathways, but their reactivity towards alkanes is strikingly different. They catalyse the metathesis of alkanes and cross-metathesis of alkanes, whereas no single-component molecular system is known to do so. Herein, we study such reactivity in terms of structure-activity relationships, to further propose a comparison to the reactivity of well-defined group 4-6 supported hydrides, focused on the alkane metathesis and alkane hydrogenolysis processes. There, the formation of intermediates containing alkylidenes and alkylidynes nicely pinpoints their pre-eminence in the catalytic conversion of alkanes, always in agreement with the elementary steps of molecular organometallic chemistry. Finally, a number of relevant reactions where the formation of alkylidene/alkylidyne intermediates has been presumed are also presented.     

Recent advances in the catalytic conversion of CO_2 to value added compunds

CO2 is a major greenhouse gas,and it can also be used as a chemical feedstock for synthesis of chemicals and fuels by passing the petrochemical source.Herein,we present the recent progress of our research work in the catalytic conversion of CO2 to chemicals,with particular attention paid to catalytic reactivity and reaction mechanism.We also give the recommendations regarding the challenges and potential directions of the future research in this field.     

NiSe2-CoSe2 with a Hybrid Nanorods and Nanoparticles Structure for Efficient Oxygen Evolution Reaction

Hetero-structure induced high performance catalyst for oxygen evolution reaction(OER)in the water splitting reaction has received increased attention.Herein,we demonstrated a novel catalyst system of NiSe₂-CoSe₂ consisting of nanorods and nanoparticles for the efficient OER in the alkaline electrolyte.This catalyst system can be easily fabricated via a low-temperature selenization of the solvothermal synthesized NiCo(OH)x precursor and the unique morphology of hybrid nanorods and nanoparticles was found by the electron microscopy analysis.The high valence state of the metal species was indicated by X-ray photoelectron spectroscopy study and a strong electronic effect was found in the NiSe₂-CoSe₂ catalyst system compared to their counterparts.As a result,NiSe₂-CoSe₂ exhibited high catalytic performance with a low overpotential of 250 mV to reach 10 mA·cm^-2 for OER in the alkaline solution.Furthermore,high catalytic stability and catalytic kinetics were also observed.The superior performance can be attributed to the high valence states of Ni and Co and their strong synergetic coupling effect between the nanorods and nanoparticles,which could accelerate the charge transfer and offer abundant electrocatalytic active sites.The current work offers an efficient hetero-structure catalyst system for OER,and the results are helpful for the catalysis understanding.     

Bipolar electrochemical mechanism for the propulsion of catalytic nanomotors in hydrogen peroxide solutions

Bimetallic nanorods are propelled in aqueous solutions by the catalytic decomposition of hydrogen peroxide to oxygen and water. Several mechanisms (interfacial tension gradients, bubble recoil, viscous Brownian ratchet, self-electrophoresis) have been proposed for the transduction of chemical to mechanical energy in this system. From Tafel plots of anodic and cathodic hydrogen peroxide reactions at various metal (Au, Pt, Rh, Ni, Ru, and Pd) ultramicroelectrodes, we determine the potential at which the anodic and cathodic reaction rates are equal for each metal. These measurements allow one to predict the direction of motion of all possible bimetallic combinations according to the bipolar electrochemical (or self-electrophoretic) mechanism. These predictions are consistent with the observed direction of motion in all cases studied, providing strong support for the mechanism. We also find that segmented nanorods with one Au end and one poly(pyrrole) end containing catalase, an enzyme that decomposes hydrogen peroxide nonelectrochemically, perform the overall catalytic reaction at a rate similar to that of nanorods containing Au and Pt segments. However, in this case there is no observed axial movement, again supporting the bipolar electrochemical propulsion mechanism for bimetallic nanorods.     

Disentangling Reaction Processes of Zeolites within Single‐Oriented Channels

Establishing structure–reactivity relationships for specific channel orientations of zeolites is vital to developing new, superior materials for various applications, including oil and gas conversion processes. Herein, a well‐defined model system was developed to build structure–reactivity relationships for specific zeolite‐channel orientations during various catalytic reaction processes, for example, the methanol‐ and ethanol‐to‐hydrocarbons (MTH and ETH) process as well as oligomerization reactions. The entrapped and effluent hydrocarbons from single‐oriented zeolite ZSM‐5 channels during the MTH process were monitored by using operando UV/Vis diffuse reflectance spectroscopy (DRS) and on‐line mass spectrometry (MS), respectively. The results reveal that the straight channels favor the formation of internal coke, promoting the aromatic cycle. Furthermore, the sinusoidal channels produce aromatics, (e.g., toluene) that further grow into larger polyaromatics (e.g., graphitic coke) leading to deactivation of the zeolites. This underscores the importance of careful engineering of materials to suppress coke formation and tune product distribution by rational control of the location of zeolite acid sites and crystallographic orientations.     

Accelerated Discovery in Photocatalysis using a Mechanism‐Based Screening Method

Herein, we report a conceptually novel mechanism‐based screening approach to accelerate discovery in photocatalysis. In contrast to most screening methods, which consider reactions as discrete entities, this approach instead focuses on a single constituent mechanistic step of a catalytic reaction. Using luminescence spectroscopy to investigate the key quenching step in photocatalytic reactions, an initial screen of 100 compounds led to the discovery of two promising substrate classes. Moreover, a second, more focused screen provided mechanistic insights useful in developing proof‐of‐concept reactions. Overall, this fast and straightforward approach both facilitated the discovery and aided the development of new light‐promoted reactions and suggests that mechanism‐based screening strategies could become useful tools in the hunt for new reactivity.     

借助液体透射电镜原位分析钯纳米棒的可控性氧化刻蚀

借助原位液体透射电镜,我们观察并研究了钯纳米棒溶液环境下的氧化刻蚀的微观行为及机理。通过改变钯纳米棒所处的液体环境,有效地控制了钯纳米棒的氧化刻蚀行为。由于端部具有较高的反应活性,钯纳米棒在氯化铁溶液中的氧化刻蚀会选择沿着轴向进行,具有明显的各向异性。当反应在超薄液层进行时,钯纳米棒的氧化刻蚀会变为准各向同性。这种行为是由于超薄溶液中溶解产物以及氧化物的扩散被抑制,在纳米棒端部选择性发生的氧化刻蚀会受到阻碍。最后,我们发现在钯纳米棒端部选择性沉积金,可以保护纳米棒的端部不受氧化,从而能控制刻蚀沿着钯纳米棒的径向进行。本文的研究结果对贵金属纳米晶的结构参数的精确调控以利于实际应用具有重要的意义。     

Porous Silica‐Coated Gold Nanorods: A Highly Active Catalyst for the Reduction of 4‐Nitrophenol

The successful coating of thin porous silica layers of various thicknesses [(10±1), (12±1), and (14±1) nm] on cetyl trimethylammonium bromide (CTAB) capped gold nanorods was achieved through a modified Stöber procedure. The resulting material was applied as a novel catalyst for the reduction of 4‐nitrophenol. The catalytic activities of the gold nanorods increased up to eight times after coating with a layer of porous silica and the reaction followed a zero‐order kinetics, having a rate constant as high as 2.92×10^?1 mol L^?1 min^?1. The spectral changes during the reduction reaction of 4‐nitrophenol were observed within a very short span of time and a complete conversion to 4‐aminophenol occured within 5–6 mins, including the induction period of ≈2 mins. The reusability of the catalyst was studied by running the catalytic reaction during five consecutive cycles with good efficiency without destroying the nanostructure. The methodology can be effectively applied to the development of composite catalysts with highly enhanced catalytic activity.     

Recent advances in 1D nanostructured catalysts for photothermal and photocatalytic reduction of CO2

The development of photocatalysts that can efficiently convert CO₂ into other valuable chemicals via photocatalytic and photothermal processes is critical to the current energy and climate change problems. However, low separation of charge carriers, short light absorption, and low activation of CO₂ molecules in photocatalysis limit the catalysts’ performance. Designing 1D heterostructures containing multiple materials can be a viable solution as their unique properties, such as high surface area, short diffusion paths of charge carriers, and enhanced light absorption properties, can potentially promote the reaction rate and product selectivity. In this review, we summarize the general features of heterostructures involving nanotubes, nanowires, nanorods, and nanobelts. Next, the main synthesis strategies are briefly highlighted, followed by the most important findings concerning their catalytic activity in the photothermal and photocatalytic CO₂ reduction processes. The article concludes with some of the current challenges and potential solutions.     

Plasmonic Scissors for Molecular Design

Heterogeneous catalysts play an important role in surface catalytic reactions, but selective bond breaking and control of reaction products in catalytic processes remain significant challenges. High‐vacuum tip‐enhanced Raman spectroscopy (HV‐TERS) is one of the best candidates to realize surface catalytic reactions. Herein, HV‐TERS was employed in a new method to control dissociation by using hot electrons, generated from plasmon decay, as plasmonic scissors. In this method, the N?N bond in 4,4′‐dimercaptoazobenzene was selectively dissociated by plasmonic scissors, and the reaction products formed from the radical fragment (SC₆H₅N) were controlled by varying the pH value. Under acidic conditions, p‐aminothiophenol was produced from the radical fragment by attachment of hydrogen ions, whereas under alkaline conditions, 4‐nitrobenzenethiol was obtained by attachment of oxygen ions to the substrate.