Advertisement
Chem Catalysis
This journal offers authors two options (open access or subscription) to publish research

Jul 21, 2022

Volume 2Issue 7p1499-1832
On the cover: In their work, Wojcieszak and co-workers (page 1686) studied and elucidated the composition of and chemical order in bimetallic Ni-Fe nanoparticles. They have demonstrated that reduced Ni-Fe nanoparticles exhibit a gradient of Ni concentration from a Ni-enriched core to Ni-depleted, Fe-enriched outer shells, making the nominal composition of the nanoparticles a poor descriptor to rationalize their catalytic performance. In addition, a permanent dealloying and redistribution of the two metals is avoided upon exposure to oxidative atmosphere. This study brings novelty to the domain by drawing conclusions from a series of Ni-Fe/SiO2 catalysts presenting very similar characteristics, save for the Ni-Fe proportions, and avoiding biases linked to discrepancies in particle size or individual composition. Image credit: Ella Maru Studio, Charleston, SC, USA....
On the cover: In their work, Wojcieszak and co-workers (page 1686) studied and elucidated the composition of and chemical order in bimetallic Ni-Fe nanoparticles. They have demonstrated that reduced Ni-Fe nanoparticles exhibit a gradient of Ni concentration from a Ni-enriched core to Ni-depleted, Fe-enriched outer shells, making the nominal composition of the nanoparticles a poor descriptor to rationalize their catalytic performance. In addition, a permanent dealloying and redistribution of the two metals is avoided upon exposure to oxidative atmosphere. This study brings novelty to the domain by drawing conclusions from a series of Ni-Fe/SiO2 catalysts presenting very similar characteristics, save for the Ni-Fe proportions, and avoiding biases linked to discrepancies in particle size or individual composition. Image credit: Ella Maru Studio, Charleston, SC, USA.

In This Issue

  • In this issue

    In This Issue highlights the most exciting articles of the current issue with short editorial pieces written by the corresponding handling editors.

Activity

  • Sacrificial agents for photocatalytic hydrogen production: Effects, cost, and development

    • Tierui Zhang,
    • Siyu Lu
    In this Activity article, Tierui Zhang (professor at the Technical Institute of Physics and Chemistry of the Chinese Academy of Sciences) and Siyu Lu (research-team professor at Zhengzhou University) introduce the effects, cost, and development of sacrificial agents for photocatalytic H2 production and discuss the opportunities and challenges of photocatalytic H2 production coupled with the conversion of sacrificial agents to value-added chemicals.
  • Strategies for designing efficient electrocatalytic HER catalysts at the atomic scale

    • Siyu Lu,
    • Tierui Zhang
    In this Activity article, Siyu Lu (research-stream professor at Zhengzhou University) and Tierui Zhang (professor at the Technical Institute of Physics and Chemistry of the Chinese Academy of Sciences) introduce the development prospects, effect, and cost of electrocatalytic hydrogen production and discuss strategies for designing efficient electrocatalytic hydrogen evolution catalysts from the atomic-structure level.

Previews

  • The rationalized correlation between selectivity and the surface ensemble site of the bimetallic catalyst

    • Lingzhen Zeng,
    • Xingwu Liu,
    • Ding Ma
    In this issue of Chem Catalysis, Shi et al. applied a combination of element-specific and surface-specific characterization techniques to conclude the minimum Ni domain fraction required for furan hydrogenation. As a glimpse of the “ensemble effect,” it provides an excellent example for studying the surface segregation of metallic catalysts.
  • Catalytic activity of bimetallic Rh/Rh-M nanosheets governed by CO spillover

    • Zhiwei Hu,
    • Linjuan Zhang
    In this issue of Chem Catalysis, Huang and co-workers constructed a series of Rh/Rh-M (M = Co, Mn, Fe, and Ni) catalysts with unique nanosheet structure, exhibiting superior anti-CO poisoning and ethanol oxidation reaction activity. This study opens a promising path to manipulating the intermediate species via CO spillover.
  • Photocatalytic production of hydrogen peroxide at high throughput

    • Hadis Yarahmadi,
    • Ali Seifitokaldani
    In this issue of Chem Catalysis, Heng Zhao et al. describe a computational investigation and synthesis of a novel photocatalyst that achieves a high production rate of 5.57 mM/h of hydrogen peroxide. After obtaining the successful high production rate, they performed a techno-economic analysis to evaluate their system’s profitability according to the current market.
  • Polarization-induced exciton dissociation in COF photocatalyst

    • Yu-Xia Li,
    • Wonyong Choi
    The regulation of the exciton properties is crucial for enhancing the activities of polymeric photocatalysts. In this issue of Chem Catalysis, Wang’s group introduces an interesting strategy that integrating ionic moieties into a covalent organic framework (COF) can increase the dielectric constant of the organic semiconductor, facilitate the exciton dissociation, and thereby boost visible-light-driven photocatalytic production of hydrogen peroxide as a solar fuel from reducing dioxygen.
  • Ni-Ir/MgAl2O4 for balanced carbon deposition-elimination in methane dry reforming

    • Ning Yan
    In this issue of Chem Catalysis, Zhao and co-workers developed a Ni-Ir/MgAl2O4 alloy catalyst offering comparable rates of CH4 dissociation and CO2 activation to avoid carbon deposition, a major undesired side reaction in methane dry reforming.
  • Stretching C-H bond in methane by solid frustrated Lewis pairs

    • Jiankang Zhao,
    • Han Yan,
    • Jie Zeng
    In this issue of Chem Catalysis, Ma et al. proposed a combination strategy by doping p-type metals and hydrogenation to construct the solid frustrated Lewis pairs (FLPs) on TiO2 toward photo-driven non-oxidative coupling of methane (NOCM). The modulation of acid-base properties on metal oxides have widened the strategies for selective Csp3–H bond activation.
  • Combining olefin borylation with carbonylation under the catalysis of copper(I)

    • Bartolo Gabriele
    In the July issue of Chem, Wu et al. describe a very interesting new catalytic process, which allows, under mild conditions and under the promotion of non-noble metal Cu(I), the one-step preparation of γ-boryl esters in a multicomponent fashion starting from β-substituted styrenes, bis(pinacolato)diboron (B2pin2), carbon monoxide, and an alcohol.
  • Stereodivergent access to rocaglaol enabled by dual catalytic asymmetric allylation

    • Byungjun Kim,
    • Sarah Yunmi Lee
    In a recent issue of Chem, Liu and Feng et al. report a stereodivergent allylation of benzofuran-3(2H)-one catalyzed by two chiral metal catalysts, a phosphoramidite-Ir complex and an N,N′-dioxide-ligated Lewis acid, and its application to the selective total synthesis of eight stereoisomers of rocaglaol, one of the flavagline-family bioactive molecules.
  • Sodium phosphides as efficient and sustainable catalysts for hydrophosphination of alkynes

    • Sobi Asako
    As the most abundant alkali metal on Earth, sodium is gaining increasing attention as a sustainable alternative to rarer lithium. Recently, in Cell Reports Physical Science, Mulvey and co-workers synthesized a series of sodium diphenylphosphides with Lewis base donors and demonstrated their use as efficient catalysts for hydrophosphination of alkynes.
  • New era of sustainable design for molecular motors

    • Gyorgy Szekely
    Native lignocellulose can be used to create light-driven molecular motors via a “green” synthetic approach. In the May issue of Green Chemistry, Barta, Feringa, and co-workers provided new insights into the sustainable design of molecular motors through reductive catalytic fractionation using a lignocellulose platform.

Perspectives

  • Vitamin B12: An efficient cobalt catalyst for sustainable generation of radical species

    • Maciej Giedyk,
    • Dorota Gryko
    Vitamin B12 is a natural cobalt complex that plays a vital role in DNA synthesis, the functioning of the nervous system, the formation of red blood cells, etc. Its activity, however, is not limited to processes taking place under physiological settings. In this perspective, we discuss the use of vitamin B12 as a catalyst for sustainable organic synthesis. We highlight its propensity to generate C-centered radicals and present the underlying mechanistic principles. Additional challenges for future discoveries are outlined.
  • Oxygen vacancies role in thermally driven and photon driven catalytic reactions

    • Hicham Idriss
    Oxygen vacancies are of considerable importance in catalytic reactions of oxides. While in a thermally driven reaction of oxygen containing compounds, heat and/or chemical energy provide the needed energy to make them again, photons with 2–3 eV energy cannot reduce back the oxide. Therefore, the prior made vacancies of oxide catalysts would be removed irreversibly. Ensuring that the reaction is indeed catalytic is a requirement for CO2 reduction and pure water splitting.

Reviews

  • Surface engineering of Cu catalysts for electrochemical reduction of CO2 to value-added multi-carbon products

    • Hassina Tabassum,
    • Xiaoxuan Yang,
    • Ruqiang Zou,
    • Gang Wu
    Surface engineering is crucial to enhance the selectivity and activity for the efficient CO2 reduction reaction (CO2RR) to a particular C2+ product. This review recaptures recent progress on the surface engineering of Cu-based catalysts as the most extensively studied metal for the CO2RR, holding the great promise of neutralizing the carbon in the environment. Furthermore, how the optimized surface, phase effects, morphology, and configuration influence the catalytic performance and the reasons for Cu catalysts' instability are also discussed.
  • Highly efficient CeO2-supported noble-metal catalysts: From single atoms to nanoclusters

    • Han Yan,
    • Ningqiang Zhang,
    • Dingsheng Wang
    We summarize the recent progress of highly efficient catalysts where noble-metal single atoms or nanoclusters are supported on CeO2. The uniqueness of applying CeO2 supports for noble-metal sites is discussed, as well as the synthetic strategies. The extraordinary catalytic performances of highly dispersed noble-metal sites on CeO2 are carefully summarized for many reactions. Perspectives and challenges are discussed as guidance for the future development in this field.
  • Recent status and challenging perspective of high entropy oxides for chemical catalysis

    • Yi Wang,
    • Jinxing Mi,
    • Zhong-Shuai Wu
    High entropy oxides (HEOs) have attracted wide interest for chemical catalysis owing to abundant active sites, adjustable specific surface area, stable crystal structure, extraordinary geometric compatibility, and unique electronic balance factors, exhibiting huge potential value for commercial exploitation. Here, the recent progress and current challenges of HEOs from the typical synthetic strategies, unique structural features, and intrinsic properties to applications in both thermocatalysis and electrocatalysis are comprehensively summarized. In brief, the HEOs obtained by different synthetic strategies, along with their structural features and derived physical-chemical properties endowed by the entropy-driven effect, allow them with highly efficient catalytic application performance. More important, the remarkable enhancement of catalytic performance based on the pure and modified HEOs are discussed by analyzing reaction mechanisms to further motivate the development in this emerging field. Finally, the future directions and challenging perspectives for chemical catalysis over HEOs are also put forward.
  • Recent progress on MTO reaction mechanisms and regulation of acid site distribution in the zeolite framework

    • Sen Wang,
    • Zhangfeng Qin,
    • Mei Dong,
    • Jianguo Wang,
    • Weibin Fan
    Methanol to olefins (MTO) is an industrially important non-petroleum route to produce value-added commodity chemicals. A challenging area in MTO is the initial conversion of C–O bonds to C–C bonds (i.e., the first C–C bond formation mechanism and the regulation of product distribution). Here the recent progress achieved in MTO reaction mechanisms and the design and development of a highly efficient zeolite catalyst through controllable regulation of acid site distribution in a framework are reviewed.

Articles

  • Probing the core and surface composition of nanoalloy to rationalize its selectivity: Study of Ni-Fe/SiO2 catalysts for liquid-phase hydrogenation

    • Dichao Shi,
    • Achraf Sadier,
    • Jean-Sébastien Girardon,
    • Anne-Sophie Mamede,
    • Carmen Ciotonea,
    • Maya Marinova,
    • Lorenzo Stievano,
    • Moulay T. Sougrati,
    • Camille La Fontaine,
    • Sébastien Paul,
    • Robert Wojcieszak,
    • Eric Marceau
    The synergy between two metals is a key parameter to selectively convert bio-sourced molecules to highly valued chemicals. However, to do that, the distribution of base metals in bimetallic structures must be controlled. We showed that alloying nickel and iron, two of the most common metals, permited us to obtain stable and very active catalyst. A detailed characterization of the materials provides useful insight into the surface composition needed to understand the high catalytic reactivity and selectivity of Ni-Fe structures.
  • CO spillover on ultrathin bimetallic Rh/Rh-M nanosheets

    • Ling Li,
    • Mingyu Chu,
    • Ruru Song,
    • Shangheng Liu,
    • Guomian Ren,
    • Yong Xu,
    • Lu Wang,
    • Qingfeng Xu,
    • Qi Shao,
    • Jianmei Lu,
    • Xiaoqing Huang
    A facile strategy for fabricating the ultrathin Rh/Rh-M (M = Co, Mn, Fe, and Ni) nanosheets were proposed. Owing to the unique structures, CO can spillover from the Rh site to the M site on ultrathin Rh/Rh-M nanosheets, leading to significantly strengthened resistance to CO poisoning and enhanced ethanol-oxidation reaction performance.
  • Rational design of carbon nitride for remarkable photocatalytic H2O2 production

    • Heng Zhao,
    • Qiu Jin,
    • Mohd Adnan Khan,
    • Steve Larter,
    • Samira Siahrostami,
    • Md Golam Kibria,
    • Jinguang Hu
    Zhao et al. demonstrate an example of photocatalyst design from theoretical guidance. Solar-driven H2O2 production is improved by enhancing production efficiency and inhibiting the decomposition, providing commercial feasibility for the industrial production of H2O2.
  • Boosting exciton dissociation by regulating dielectric constant in covalent organic framework for photocatalysis

    • Guoqing Li,
    • Ping Fu,
    • Qihong Yue,
    • Fangpei Ma,
    • Xiaolong Zhao,
    • Shu Dong,
    • Xin Han,
    • Yu Zhou,
    • Jun Wang
    The high polarization of the ionic sites greatly increases the dielectric constant of the COF matrix and thus reduces the exciton binding energy, effectively accelerating the H2O2 production rate under visible-light irradiation.
  • Ultra-durable Ni-Ir/MgAl2O4 catalysts for dry reforming of methane enabled by dynamic balance between carbon deposition and elimination

    • Haocheng Li,
    • Cong Hao,
    • Jingqing Tian,
    • Shuai Wang,
    • Chen Zhao
    The highly dispersed Ni-Ir/MgAl2O4 alloy catalyst has high activity and long-period stability (600 h) with zero carbon deposition for dry reforming of methane at industrially relevant temperature (650°C). This special catalytic system follows a balance mechanism between the active sites and the carbon deposits-eliminations, where Ni played the role of activating CH4 and MgAl2O4 adsorbed CO2 to form carbonate species that can be effectively used by Ir to eliminate carbon species generated from CH4 activation on Ni.
  • Ruthenium/titanium oxide interface promoted electrochemical nitrogen reduction reaction

    • Weizheng Cai,
    • Ya-Fei Jiang,
    • Jincheng Zhang,
    • Hongbin Yang,
    • Junming Zhang,
    • Cong-Qiao Xu,
    • Wei Liu,
    • Jun Li,
    • Bin Liu
    To address the challenges of low activity and poor selectivity in the electrochemical nitrogen reduction reaction (eNRR), Ru/TiO2 with a sophisticated interface is designed and synthesized. By constructing the Ru-TiO2 interface, the valence states of Ru can be carefully modulated, resulting in promoted reaction kinetics of the eNRR with suppressed HER.
  • Design of frustrated Lewis pair in defective TiO2 for photocatalytic non-oxidative methane coupling

    • Jiayu Ma,
    • Qingqing Zhang,
    • Ziyu Chen,
    • Kai Kang,
    • Lihan Pan,
    • Shiqun Wu,
    • Chen Chen,
    • Zhiqin Wu,
    • Jinlong Zhang,
    • Lingzhi Wang
    Long LA–LB distance and strong acid and base intensities promote the stretching of the C–H bond. The effect of light irradiation on improving the intensities of LA Ga and LB Ti–OH was confirmed based on the electron transition from LA to LB, which is the key to forming methyl and hydrogen radicals for the further coupling production of C2H6.
  • Photocatalytic fluoroalkylations of (hetero)arenes enabled by the acid-triggered reactivity umpolung of acetoxime esters

    • Min Zhang,
    • Jing Chen,
    • Shijun Huang,
    • Biping Xu,
    • Jin Lin,
    • Weiping Su
    An ongoing challenge in trifluoromethylation reaction is the use of less expensive and more practical trifluoromethyl sources. We describe herein a general photocatalytic method for regioselective C–H fluoroalkylation of (hetero)arenes and olefines that uses readily available fluoroalkyl carboxylic anhydrides as fluoroalkylating reagents in the presence of simple acetoxime as an activator. The success achieved in the development of such a method is attributed to the discovery of the unprecedented acid-triggered reactivity umpolung of acetoxime ester toward single-electron reduction-induced cleavage of N–O σ bond.
  • Direct electro-synthesis of valuable C=N compound from NO

    • Xianhao Zhang,
    • Huijuan Jing,
    • Shiming Chen,
    • Bing Liu,
    • Liang Yu,
    • Jianping Xiao,
    • Dehui Deng
    This work reports the direct electrochemical hydrogenative coupling of NO and cyclohexanone (e-HCNC) for synthesizing cyclohexanone oxime (CHO) by using water as the hydrogen source over a carbon catalyst under ambient conditions. The strategy combines electrocatalytic hydrogenative removal of NO with oximation of cyclohexanone and enables recycling of the waste gas in producing high-value CHO with a simple one-step process.
  • Accelerating catalyst development for biofuel production through multiscale catalytic fast pyrolysis of biomass over Mo2C

    • Calvin Mukarakate,
    • Kristiina Iisa,
    • Susan E. Habas,
    • Kellene A. Orton,
    • Mengze Xu,
    • Connor Nash,
    • Qiyuan Wu,
    • Renee M. Happs,
    • Richard J. French,
    • Anurag Kumar,
    • Elisa M. Miller,
    • Mark R. Nimlos,
    • Joshua A. Schaidle
    Accelerating the catalyst-process development cycle for complex chemistries, especially biomass processing, requires multiscale studies spanning model compound experiments to integrated, bench-scale tests with realistic feedstocks.
Advertisement
Advertisement